CN113549414A - Preparation method of environment-friendly nano-cellulose crosslinked dopa adhesive - Google Patents
Preparation method of environment-friendly nano-cellulose crosslinked dopa adhesive Download PDFInfo
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- CN113549414A CN113549414A CN202110916678.4A CN202110916678A CN113549414A CN 113549414 A CN113549414 A CN 113549414A CN 202110916678 A CN202110916678 A CN 202110916678A CN 113549414 A CN113549414 A CN 113549414A
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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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
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/02—Cellulose; Modified cellulose
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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
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/02—Cellulose; Modified cellulose
- C09J101/04—Oxycellulose; Hydrocellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the field of adhesive preparation, and particularly relates to a preparation method of an environment-friendly nano cellulose crosslinked dopa adhesive. Firstly, a protected dopa adhesive is obtained by copolymerizing a protected dopa monomer and an acrylic monomer. And removing and protecting the protected dopa adhesive to obtain the dopa adhesive. And finally, blending and crosslinking the dopa adhesive and the nanocellulose to obtain the environment-friendly nanocellulose crosslinked dopa adhesive. The dopa monomer and the acrylic monomer are copolymerized and then blended and crosslinked with the nanocellulose to prepare the environment-friendly nanocellulose crosslinked dopa adhesive, and the environment-friendly nanocellulose crosslinked dopa adhesive can be applied to the fields of biomedical treatment, tissue engineering, furniture, buildings, electronic industry and the like.
Description
Technical Field
The invention relates to a preparation method of a dopa adhesive, in particular to a preparation method of a reusable environment-friendly conductive adhesive.
Background
Adhesives are substances that can bond objects to be bonded together by adhesion, and are widely used in daily life. Nowadays, people mainly use adhesives of synthetic resins such as urea-formaldehyde glue, phenol-formaldehyde glue, epoxy resin, melamine resin and the like, but the adhesives have the defects of harming the environment and the human health and the like. Therefore, the development of an adhesive with environmental protection, health, no toxicity and excellent adhesive performance is a problem to be solved urgently.
The catechol group of the dopa has excellent biocompatibility and adhesion performance, and can be used for preparing a dopa adhesive by polymerization. The nano-cellulose is a common organic polymer, and has the advantages of easy obtainment, environmental friendliness, excellent biocompatibility and the like. The invention uses nano-cellulose to crosslink the dopa adhesive to prepare the nontoxic and harmless dopa adhesive, and is applied to the fields of biological medicine, tissue engineering, furniture, buildings, electronic industry and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly nano cellulose crosslinked dopa adhesive.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an environment-friendly nano-cellulose crosslinked dopa adhesive comprises the following steps:
(1) preparation of dopa adhesive: adding dopa monomer and acrylic monomer into mixed solution of ethanol and azobisisobutyronitrile, and reacting in the presence of N2Copolymerizing for 14 hours at 70 ℃ under the condition to obtain a protected dopa adhesive, and finally deprotecting by using hydrochloric acid to obtain the dopa adhesive;
(2) preparing a nano-cellulose crosslinked dopa adhesive: dissolving the dopa adhesive prepared in the step (1) with ethanol, adding nanocellulose into a dopa adhesive solution, and stirring at normal temperature to prepare the environment-friendly nanocellulose crosslinked dopa adhesive.
The molar ratio of the dopa monomer to the acrylic monomer in the step (1) is 1: 9. the molar ratio of the dopa monomer to ethanol is 1: 170-1000, wherein the molar ratio of the dopa monomer to the azobisisobutyronitrile is 1: 0.5 to 3.0.
Further, the dopa monomer comprises any one of dopamine acrylamide and dopamine methacrylamide (the reference is H.Xu, ACS Macro Letters,2012,1(4): 457-.
Further, the acrylic monomer comprises any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and 2-hydroxybutyl methacrylate.
Further, the nano-cellulose includes any one of cellulose nanocrystals, microcrystalline cellulose, bacterial nano-cellulose, TEMPO oxidized nano-cellulose (reference A. Isogai, Nanoscale,2011,3(1):71-85 synthesis).
Further, the molar percentage of the dopa monomer unit is 1-33%.
Further, the content of the nano-cellulose is 0.1-1.0 wt%.
The invention has the advantages that: the dopa adhesive is prepared by copolymerizing a dopa monomer and an acrylic monomer through free radical polymerization, and then blending and crosslinking the dopa adhesive and nanocellulose, so that the adhesive is environment-friendly and strong in adhesiveness.
Drawings
FIG. 1 is a schematic reaction diagram of dopa-adhesive.
Figure 2 adhesive strength for different nanocellulose contents.
FIG. 3CCK-8 detects cell proliferation on the adhesive.
Detailed Description
Example 1
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.045g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose cross-linked environment-friendly dopa adhesive.
Example 2
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.095g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
Example 3
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.148g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
Example 4
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2Reacting at 70 ℃ for 14 hours,then precipitating with diethyl ether and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.207g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
Example 5
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.272g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
Example 6
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.344g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
Example 7
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.423g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
Example 8
0.45g (1mmol) of DOPAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol0.164g of azobisisobutyronitrile was added thereto, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.512g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
Example 9
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.612g of nano-cellulose solution is added into the ethanol, and the solution is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
Example 10
0.45g (1mmol) of DOPAMAcrylamide and 1.035g (9mmol) of hydroxyethyl methacrylate were added to 30mL of ethanol, 0.164g of azobisisobutyronitrile was further added, and N was charged thereto2And reacting at 70 ℃ for 14 hours, precipitating with diethyl ether, and drying in vacuum to obtain the dopa adhesive.
0.3g of dopa adhesive is weighed and dissolved in 1mL of ethanol, 0.726g of nano-cellulose solution is added into the ethanol, and the mixture is stirred for 10 minutes to prepare the nano-cellulose crosslinked environment-friendly dopa adhesive.
The dopa adhesive prepared by the invention has strong adhesive strength and good environmental protection.
The dopa adhesive prepared in the above example was subjected to a tack strength test. The adhesive strength was the strongest as measured on stainless steel substrate, followed by wood, aluminum sheet, glass in that order, and the weakest as plastic. For a plastic base material, the nanocellulose is added into the adhesive, and the influence on the adhesive strength of the adhesive is not obviously changed. However, for glass, wood, aluminum sheets and stainless steel substrates, the addition of nanocellulose into the adhesive has obvious changes on the adhesive strength of the adhesive. The adhesive strength of the nano-crystalline cellulose is gradually enhanced along with the gradual increase of the content of the nano-crystalline cellulose. The adhesive strength was maximized when the nanocellulose content was 0.5wt%, 2.05MPa, 2.50MPa, 2.75MPa and 5.50MPa on glass, aluminum sheet, wood and stainless steel, respectively, with the strongest (5.50MPa) on stainless steel substrates. However, as the nanocellulose content continued to increase, the adhesive strength gradually decreased instead (fig. 2). This result indicates that nanocellulose-crosslinked adhesives can increase their adhesive strength.
The dopa adhesive prepared in the above example was subjected to biocompatibility test. For experimental evaluation with NIH 3T3 cells, a small patch of glue (1 × 1 × 2mm) was washed with deionized water and PBS buffer, then sterilized with uv light for 30 minutes, and finally cultured in cells. After 1 and 5 days of culture, the cell growth on the adhesive was examined with CCK-8. After 1 day of culture, the relative survival rate of the cells is about 93.0% similar to that of the control group, but after 5 days of culture, the relative survival rate of the cells of the control group is 260%, and the relative survival rate of the dopa adhesive and the dopa adhesive crosslinked by the nanocellulose is 290%, which indicates that the dopa adhesive crosslinked by the nanocellulose is non-toxic and harmless to the environment and human health and has excellent environmental protection property (fig. 3).
Claims (8)
1. A preparation method of an environment-friendly nano-cellulose crosslinked dopa adhesive is characterized by comprising the following steps: is prepared by the following steps:
(1) preparing a dopa adhesive: adding dopa monomer and acrylic monomer into mixed solution of ethanol and azobisisobutyronitrile, and reacting in the presence of N2Copolymerizing for 14 hours at 70 ℃ under the condition to obtain the dopa adhesive;
(2) preparing a nano-cellulose crosslinked dopa adhesive: dissolving the dopa adhesive prepared in the step (1) with ethanol, adding nanocellulose into a dopa adhesive solution, and stirring at normal temperature to prepare the environment-friendly nanocellulose crosslinked dopa adhesive.
2. The method for preparing the environment-friendly nanocellulose-crosslinked dopa adhesive according to claim 1, characterized in that: the molar ratio of the dopa monomer to the acrylic monomer in the step (1) is 1: 9. the molar ratio of the dopa monomer to ethanol is 1: 170-1000, wherein the molar ratio of the dopa monomer to the azobisisobutyronitrile is 1: 0.5 to 3.0.
3. The environment-friendly nanocellulose-crosslinked dopa adhesive of claim 1, characterized by: the dopa monomer comprises any one of dopamine acrylamide and dopamine methacrylamide.
4. The environment-friendly nanocellulose-crosslinked dopa adhesive of claim 1, characterized by: the acrylic monomer comprises any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and 2-hydroxybutyl methacrylate.
5. The environment-friendly nanocellulose-crosslinked dopa adhesive of claim 1, characterized by: the nano-cellulose comprises any one of cellulose nanocrystals, microcrystalline cellulose, bacterial nano-cellulose and TEMPO oxidized nano-cellulose.
6. The environment-friendly nanocellulose-crosslinked dopa adhesive of claim 1, characterized by: the molar percentage of the dopa monomer unit is 1-33%.
7. The environment-friendly nanocellulose-crosslinked dopa adhesive of claim 1, characterized by: the content of the nano-cellulose is 0.1-1.0 wt%.
8. The environment-friendly nanocellulose-crosslinked dopa adhesive of claim 6, characterized by: the content of the nanocellulose was 0.5 wt%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134754A (en) * | 2018-07-25 | 2019-01-04 | 重庆工程职业技术学院 | A kind of antibacterial micro-nano particle and its preparation method and application having adhesive function |
| CN110010896A (en) * | 2019-04-03 | 2019-07-12 | 北京科技大学 | A kind of lithium ion battery ionic conduction type cross-linked binder and preparation method thereof |
| KR102158446B1 (en) * | 2020-04-17 | 2020-09-21 | 김홍철 | Method for Manufacturing Nail polish sticker |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134754A (en) * | 2018-07-25 | 2019-01-04 | 重庆工程职业技术学院 | A kind of antibacterial micro-nano particle and its preparation method and application having adhesive function |
| CN110010896A (en) * | 2019-04-03 | 2019-07-12 | 北京科技大学 | A kind of lithium ion battery ionic conduction type cross-linked binder and preparation method thereof |
| KR102158446B1 (en) * | 2020-04-17 | 2020-09-21 | 김홍철 | Method for Manufacturing Nail polish sticker |
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