CN111087952B - Preparation method of water-resistant cellulose-based adhesive - Google Patents
Preparation method of water-resistant cellulose-based adhesive Download PDFInfo
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- CN111087952B CN111087952B CN202010067292.6A CN202010067292A CN111087952B CN 111087952 B CN111087952 B CN 111087952B CN 202010067292 A CN202010067292 A CN 202010067292A CN 111087952 B CN111087952 B CN 111087952B
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
Abstract
The invention provides a preparation method of a water-resistant cellulose-based adhesive, which comprises the steps of firstly reacting 2-bromoisobutyryl bromide with cellulose to generate a cellulose-based macroinitiator, then graft polymerizing dopa monomers and acrylic monomers onto the cellulose-based macroinitiator to obtain a protected water-resistant cellulose-based adhesive, and then removing the protection of the protected water-resistant cellulose-based adhesive to obtain the water-resistant cellulose-based adhesive. The invention uses cellulose as a base material, and functional groups such as catechol are grafted on the cellulose, so that the adhesive can have good adhesive property in a humid environment or water, and can be applied to the fields of biological medicine, tissue engineering, electronics and the like.
Description
Technical Field
The invention relates to an adhesive, in particular to a water-resistant cellulose-based adhesive.
Background
The adhesive can connect two or more workpieces or materials together through the actions of adhesion, cohesion and the like of an interface, has the characteristics of continuous stress distribution, light weight, good sealing property and the like, and is widely applied to daily life. At present, people mainly use adhesives of synthetic resins such as urea-formaldehyde glue, phenol-formaldehyde glue, melamine-formaldehyde glue and the like, but the adhesives have the defects of certain toxicity, poor water resistance and the like. Therefore, the development of an adhesive with environment-friendly, healthy, non-toxic and excellent water resistance is an urgent problem to be solved in human life and industrial production.
Cellulose is a natural organic polymer rich in nature, exists in green plants and marine organisms in large quantity, and has the advantages of low price, easy obtainment, environmental friendliness, excellent biocompatibility and the like. The catechol group of dopa has excellent biocompatibility, water resistance and adhesion performance, and can be used for preparing adhesives by graft polymerization. The invention chemically modifies cellulose, grafts dopa monomer, prepares nontoxic and harmless water-resistant cellulose-based adhesive, and is applied to the fields of tissue engineering, medical treatment, electronics and the like.
Disclosure of Invention
The invention aims to provide an environment-friendly, healthy and nonhazardous water-resistant cellulose-based adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a water-resistant cellulose-based adhesive comprises the following steps:
a. synthesis of cellulose-based macroinitiator: cellulose is treated with lithium chlorideN,NAfter dissolving dimethylacetamide, dropwise adding pyridine and 2-bromine isobutyryl bromide, reacting at normal temperature for 24 hours, filtering, and drying in vacuum to obtain a bromine-containing cellulose-based macroinitiator;
b. preparation of a water-resistant cellulose-based adhesive: b, adding the bromine-containing cellulose base macroinitiator prepared in the step a, the dopa monomer and the acrylic acid monomer into the mixtureN,N-dimethylformamide, cuprous bromide,N,N,N',N',N' -pentamethyldiethyleneIn a mixed solution of the base triamine, in N2Carrying out copolymerization at 60 ℃ under the condition to obtain a protected adhesive, and carrying out deprotection by using hydrochloric acid to obtain the water-resistant cellulose-based adhesive.
The molar ratio of the cellulose, pyridine and 2-bromine isobutyryl bromide used in the step a is 1:5: 5; the substitution degree of the prepared bromine-containing cellulose-based macroinitiator is 0.3-1.5.
And b, converting the use amounts of the bromine-containing cellulose-based macroinitiator, the dopa monomer and the acrylic acid monomer according to the molar ratio of the number of glucose units in the bromine-containing cellulose-based macroinitiator to the dopa monomer and the acrylic acid monomer of 1 (1-3) to (6-18). Wherein the dopa monomer comprises dopamine acrylamide and dopamine methacrylamide. The acrylic monomer comprises methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate.
B bromine-containing cellulose-based macroinitiator used in step b andN,N-dimethylformamide, cuprous bromide,N,N,N',N',N' -pentamethyldiethylenetriamine in a molar ratio of 1:1: 3.
The invention has the advantages that: the invention utilizes cellulose as a base material, and dopes monomers and acrylic monomers are copolymerized and grafted on the cellulose in a covalent bond mode, so that the cellulose has good bonding and water resistance.
Drawings
FIG. 1 is a structural formula of the water-resistant cellulose-based adhesive prepared by the invention.
Detailed Description
The preparation method of the water-resistant cellulose-based adhesive comprises the following steps:
a. synthesis of cellulose-based macroinitiator: lithium chloride for celluloseN,NAfter dissolving dimethylacetamide, dropwise adding pyridine and 2-bromine isobutyryl bromide, reacting at normal temperature for 24 hours, filtering, and drying in vacuum to obtain a bromine-containing cellulose-based macroinitiator;
b. preparation of a water-resistant cellulose-based adhesive: b, adding the bromine-containing cellulose base macroinitiator prepared in the step a, the dopa monomer and the acrylic acid monomer into the mixtureN,N-dimethylformamide, cuprous bromide,N,N,N',N',N'' -pentamethyldiethylenetriamine in N2And (3) carrying out copolymerization at 60 ℃ under the condition to obtain a protected adhesive, and finally carrying out deprotection by using hydrochloric acid to obtain the water-resistant cellulose-based adhesive.
The molar ratio of the cellulose, pyridine and 2-bromine isobutyryl bromide used in the step a is 1:5: 5; the substitution degree of the prepared bromine-containing cellulose-based macroinitiator is 0.3-1.5.
And b, converting the use amounts of the bromine-containing cellulose-based macroinitiator, the dopa monomer and the acrylic acid monomer according to the molar ratio of the number of glucose units in the bromine-containing cellulose-based macroinitiator to the dopa monomer and the acrylic acid monomer of 1 (1-3) to (6-18). Wherein the dopa monomer comprises dopamine acrylamide and dopamine methacrylamide. The acrylic monomer comprises methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate.
B bromine-containing cellulose-based macroinitiator used in step b andN,N-dimethylformamide, cuprous bromide,N,N,N',N',N' -pentamethyldiethylenetriamine in a molar ratio of 1:1: 3.
The cellulose-based adhesive prepared by the invention has remarkable water resistance. And (3) carrying out a water resistance test on the water resistance cellulose-based adhesive prepared with different dopa contents. The test substrate is an iron sheet, the prepared adhesive is dissolved by chloroform/methanol, then the solution is coated on the surface of the iron sheet by a spin coater, the iron sheet and the iron sheet are combined and respectively placed in ultrapure water and seawater for standing for 48 hours, and then the adhesive strength of the iron sheet is measured by an experimental tensile machine. The results showed that the maximum adhesive strength measured in ultrapure water on standing was 0.20MPa, while the maximum adhesive strength measured in seawater was 0.26MPa when the dopa content was 22.4 mol%; when the dopa content is 15.0mol%, the maximum adhesive strength measured in ultrapure water while standing is 0.17MPa, and the maximum adhesive strength measured in seawater is 0.23 MPa; when the dopa content is 8.4mol%, the maximum adhesive strength measured in ultrapure water while standing is 0.15MPa, and the maximum adhesive strength measured in seawater is 0.20 MPa; when the dopa content is 5.0mol%, the maximum adhesive strength measured in ultrapure water on standing is 0.11MPa, and the maximum adhesive strength measured in seawater is 0.16 MPa. From this, it can be seen that the water-resistant effect is best when the dopa content is 22.4mol% (when the dopa charge rate exceeds 30%, it is difficult to synthesize adhesive, possibly due to steric hindrance effect).
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Adding 2g (12.4 mmol) of cellulose into 200mL of cellulose with the concentration of 5-10 g/100mLN,NHeating the mixture to 100 ℃ by using an oil-rich pot, stirring the mixture for 2 hours, and stirring the mixture for one day at normal temperature to obtain a cellulose solution. Under ice-bath conditions, 5.0mL (62.1 mmol) of pyridine and 7.7mL (62.1 mmol) of 2-bromoisobutyryl bromide were added, and the reaction was carried out at room temperature for 24 h. After the reaction is finished, 4L of absolute ethyl alcohol is used for separating out, the cellulose-based macroinitiator is obtained through vacuum drying, and the substitution degree is calculated to be 0.85.
0.311g (1 mmol) of cellulose-based macroinitiator was weighed out and dissolved in 25mLN,NDimethylformamide, after dissolution, 0.636mL (6 mmol) of methyl methacrylate and 1.35g (3 mmol) of dopa monomer are added, and 0.144g of cuprous bromide and 0.63mL of DOPA are addedN,N,N',N',N' -pentamethyldiethylenetriamine, to which N is added2And reacting at 60 ℃ for 12 hours, and finally precipitating with diethyl ether and drying in vacuum to obtain the water-resistant cellulose-based dopa adhesive with dopa content of 22.4 mol%.
Example 2
3g (18.6)mmol) cellulose is added into 250mL of cellulose with the concentration of 5-10 g/100mLN,NHeating the mixture to 100 ℃ by using an oil-rich pot, stirring the mixture for 2 hours, and stirring the mixture for one day at normal temperature to obtain a cellulose solution. Under ice-bath conditions, 7.5mL (93.1 mmol) of pyridine and 11.5mL (93.0 mmol) of 2-bromoisobutyryl bromide were added, and the reaction was carried out at room temperature for 24 h. After the reaction is finished, 5L of absolute ethyl alcohol is used for separating out, the cellulose-based macroinitiator is obtained through vacuum drying, and the substitution degree is calculated to be 0.83.
0.311g (1 mmol) of cellulose-based macroinitiator was weighed out and dissolved in 25mLN,NDimethylformamide, after dissolution, 0.742mL (7 mmol) of methyl methacrylate and 0.90g (2 mmol) of dopa monomer are added, followed by 0.144g of cuprous bromide and 0.63mLN,N,N',N',N' -pentamethyldiethylenetriamine, to which N is added2And reacting at 60 ℃ for 12 hours, and finally precipitating with diethyl ether and drying in vacuum to obtain the water-resistant cellulose-based dopa adhesive with dopa content of 15.0 mol%.
Example 3
Adding 4g (24.8 mmol) of cellulose into 300mL of cellulose with the concentration of 5-10 g/100mLN,NHeating the mixture to 100 ℃ by using an oil-rich pot, stirring the mixture for 2 hours, and stirring the mixture for one day at normal temperature to obtain a cellulose solution. Under ice-bath conditions, 10.0mL (124.1 mmol) of pyridine and 15.4mL (124.4 mmol) of 2-bromoisobutyryl bromide were added, and the reaction was carried out at room temperature for 24 h. After the reaction is finished, 6L of absolute ethyl alcohol is used for separating out, the cellulose-based macroinitiator is obtained through vacuum drying, and the substitution degree is calculated to be 0.73.
0.311g (1 mmol) of cellulose-based macroinitiator was weighed out and dissolved in 30mLN,NDimethylformamide, after dissolution, 0.848mL (8 mmol) of methyl methacrylate and 0.45g (1 mmol) of dopa monomer are added, followed by 0.144g of cuprous bromide and 0.63mLN,N,N',N',N' -pentamethyldiethylenetriamine, to which N is added2Reacting at 60 deg.C for 12 hr, precipitating with diethyl ether, and vacuum drying to obtain water-resistant cellulose-based dopa adhesive with dopa content of 8.4mol%And (3) preparing.
Example 4
Adding 5g (31.0 mmol) of cellulose into 400mL of cellulose with the concentration of 5-10 g/100mLN,NHeating the mixture to 100 ℃ by using an oil-rich pot, stirring the mixture for 2 hours, and stirring the mixture for one day at normal temperature to obtain a cellulose solution. Under ice-bath conditions, 12.5mL (155.1 mmol) of pyridine and 19.2mL (155.3 mmol) of 2-bromoisobutyryl bromide were added, and the reaction was carried out at room temperature for 24 h. After the reaction is finished, 8L of absolute ethyl alcohol is used for separating out, the cellulose-based macroinitiator is obtained through vacuum drying, and the substitution degree is calculated to be 0.78.
0.311g (1 mmol) of cellulose-based macroinitiator was weighed out and dissolved in 30mLN,NDimethylformamide, after dissolution 1.908mL (18 mmol) of methyl methacrylate and 0.45g (1 mmol) of dopa monomer, 0.144g of cuprous bromide and 0.63mL ofN,N,N',N',N' -pentamethyldiethylenetriamine, to which N is added2And reacting at 60 ℃ for 12 hours, and finally precipitating with diethyl ether and drying in vacuum to obtain the water-resistant cellulose-based dopa adhesive with dopa content of 5.0 mol%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A preparation method of a water-resistant cellulose-based adhesive is characterized by comprising the following steps: the method comprises the following steps:
a. synthesis of cellulose-based macroinitiator: cellulose is treated with lithium chlorideN,NAfter dissolving dimethylacetamide, dropwise adding pyridine and 2-bromine isobutyryl bromide, reacting at normal temperature for 24 hours, filtering, and drying in vacuum to obtain a bromine-containing cellulose-based macroinitiator;
b. preparation of a water-resistant cellulose-based adhesive: b, adding the bromine-containing cellulose base macroinitiator prepared in the step a, the dopa monomer and the acrylic acid monomer into the mixtureN,N-dimethylformamide, cuprous bromide,N,N,N',N',N'' -pentamethyldiethylenetriamine in the mixed solutionIn N at2Carrying out copolymerization at 60 ℃ under the condition to obtain a protected adhesive, and carrying out deprotection by using hydrochloric acid to obtain the water-resistant cellulose-based adhesive;
and b, converting the use amounts of the bromine-containing cellulose-based macroinitiator, the dopa monomer and the acrylic acid monomer according to the molar ratio of the number of glucose units in the bromine-containing cellulose-based macroinitiator to the dopa monomer and the acrylic acid monomer of 1 (1-3) to (6-18).
2. The method for preparing a water-resistant cellulose-based adhesive according to claim 1, wherein the method comprises the following steps: the molar ratio of the cellulose, pyridine and 2-bromoisobutyryl bromide used in step a is 1:5: 5.
3. The method for preparing a water-resistant cellulose-based adhesive according to claim 1, wherein the method comprises the following steps: and c, the substitution degree of the bromine-containing cellulose base macroinitiator prepared in the step a is 0.3-1.5.
4. The method for preparing a water-resistant cellulose-based adhesive according to claim 1, wherein the method comprises the following steps: the dopa monomer used in step b comprises dopa acrylamide and dopa methacrylamide.
5. The method for preparing a water-resistant cellulose-based adhesive according to claim 1, wherein the method comprises the following steps: the acrylic monomer used in step b comprises methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate.
6. The method for preparing a water-resistant cellulose-based adhesive according to claim 1, wherein the method comprises the following steps: b bromine-containing cellulose-based macroinitiator used in step b andN,N-dimethylformamide, cuprous bromide,N,N,N',N',N' -pentamethyldiethylenetrisThe molar ratio of amine is 1:1: 3.
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| CN103145918A (en) * | 2013-01-18 | 2013-06-12 | 中国林业科学研究院林产化学工业研究所 | Preparation method of cellulose-g-resin acid grafted copolymer |
| CN104558421A (en) * | 2014-10-10 | 2015-04-29 | 河北科技大学 | Preparation method of grafted cellulose medicinal molecule with pH/temperature responsiveness |
| CN108587513A (en) * | 2018-03-27 | 2018-09-28 | 福建农林大学 | A kind of cellulose base DOPA adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103145918A (en) * | 2013-01-18 | 2013-06-12 | 中国林业科学研究院林产化学工业研究所 | Preparation method of cellulose-g-resin acid grafted copolymer |
| CN104558421A (en) * | 2014-10-10 | 2015-04-29 | 河北科技大学 | Preparation method of grafted cellulose medicinal molecule with pH/temperature responsiveness |
| CN108587513A (en) * | 2018-03-27 | 2018-09-28 | 福建农林大学 | A kind of cellulose base DOPA adhesive and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Adhesive layer-by-layer films of carboxymethylated cellulose nanofibril-dopamine covalent bioconjugates inspired by marine mussel threads;Erdem Karabulut et al.;《ACS NANO》;20120529;第6卷(第6期);第4731-4739页 * |
| ATRP法制备纤维素-g-甲基丙烯酸甲酯共聚物;武荣兰 等;《新疆大学学报（自然科学版）》;20130228;第1-5,18页 * |
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