CN107345366A - A kind of universal method of quick mussel bionic surface functional modification - Google Patents
A kind of universal method of quick mussel bionic surface functional modification Download PDFInfo
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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Abstract
The invention discloses a kind of universal method of quick mussel bionic surface functional modification, belong to material surface modifying technology field.Specifically by dopamine and its derivative, oxidant, di-or higher functional reagent proportionally mixed preparing reaction solution, material that then will be to be finished, which immerses, carries out surface modification in reaction solution, finally wash, dry.The present invention has the advantages such as gentle, fast, the functionalization efficiency height of reaction speed of reaction condition, and operating procedure is simple, has universality, and prepared surface-functionalized decorative layer stability is good, has the characteristics of acid and alkali resistance and highly polar organic solvent.
Description
(1) technical field
The present invention relates to material surface modifying technology field, specifically, is related to a kind of quick mussel bionic surface function
Change the universal method of modification.
(2) background technology
Mussel is a kind of common shell-fish marine animal, and they can be glued rapidly securely by secretory protein mucus
Be attached to the body surfaces such as rock, metal, glass, inspired by this phenomenon, adhesion based on mussel byssus protein research by
The extensive concern of people.It is however, numerous there is step due to directly extracting or preparing byssus protein using gene recombination technology
Trivial, the defects of cost is higher, yield is relatively low.In order to solve these problems, 2007, Lee etc. (Science, 318,426-430)
Found by the research to mussel byssus protein, it is residual containing nearly 30% L-3,4 dihydroxyphenylalanine and 15% lysine in its amino acid sequence
Base, and propose to utilize the autohemagglutination of dopamine in the basic conditions, can be including metal, oxide, polymer, semiconductor, ceramics
Material surface Deng including realizes functional modification, from this, turns into material, chemistry, biology based on the bionical surface chemistry of mussel
The crossing research focus in the fields such as medical science.
The research of mussel bionic surface modification at present mostly by dopamine autoxidation in the basic conditions, then occur from
Poly- cross-linking reaction is realized.But the reaction speed is slower, generally requiring 24h could complete, and exist decorative layer uniformity compared with
The shortcomings of poor, acidproof alkaline stability difference, it significantly limit the application of the technology.Simultaneously as dopamine is expensive, reduce
The cost of its surface biomimetic modification is also current urgent problem to be solved.Research finds addition oxidant, can accelerate dopamine
Autoxidation speed, so as to accelerate deposition velocity, but deposition reaction process still need to 2~4 hours (Polymer Chemistry,
2010,1,1430-1433；Langmuir, 2013,29,12754-12761)；According to another report, CuSO4/H2O2The dopamine of induction
Fast deposition technology, be greatly improved depositing dopamine speed (43nm/h) (Angewandte Chemie, 2016,128：
3106-3109), it is the current most fast deposition velocity reported, and more covalent bonds substitutions is formd in oxidizing process
Non-covalent bond, coating is all significantly increased in nature in hydrophily, organic solvent-resistant, strong alkali-acid resistance etc., although Cu2+ can be assigned
The excellent bactericidal property of precoat, but this method is not suitable for biocompatibility modification, without universality.
The present invention for problem present in mussel bionic surface modification technique, propose using oxidant accelerate dopamine and
The autoxidation speed of its derivative, di-or higher functional reagent accelerates polymerization-cross-linking reaction, to improve its surface-functionalized modification
Speed and efficiency.The present invention not only accelerates the reaction speed of dopamine surface biomimetic modification technique, and can be to dopamine
Derivative is promoted, and has universality.
(3) content of the invention
The invention aims to overcome defect present in existing mussel bionics techniques, there is provided a kind of technique is simple,
The dopamine of mild condition and its accelerated surface biomimetic modification method of derivative.This method is by will " oxidation-from poly- crosslinking "
Coupling, accelerate reaction speed, and improve the universality of method.
A kind of universal method of quick mussel bionic surface functional modification, comprises the following steps：
Dopamine and its derivative, oxidant and di-or higher functional reagent are added in solvent mix according to a certain percentage
The reaction solution of certain pH value is prepared, then immerses material to be finished in reaction solution, stirring at room temperature carries out surface modification, most
Material washing, drying are taken out afterwards, obtain the functionalization material with certain decorative layer thickness.
It is an advantage of the invention that：
1) use oxidant and di-or higher functional reagent, accelerate " oxidation-from poly- crosslinking " of dopamine and its derivative
Reaction process, significantly improve reaction speed and functional modification efficiency；
2) this method has universality, can be applied to the modification of the surface such as metal, nonmetallic, macromolecule, nano material, and change
Property after material surface rich in hydroxyl, amido isoreactivity functional group, for material further be modified provide possibility.
3) this method reaction condition is gentle, simple to operate, and time-consuming short, cost is low, is easy to industrialized production and application.
(4) embodiment
Following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1
0.8g dopamine hydrochloride is dissolved in 200mL deionized water, 0.9128g persulfuric acid is added under stirring condition
Ammonium, 267 μ L ethylenediamines are configured to reaction solution, regulation pH value to 8.5, then will be cut into 1.5cm × 1.5cm or so polypropylene without
Spin cloth to immerse in above-mentioned solution, at room temperature stirring reaction 20min.After the completion of modification, non-woven fabrics, 60 DEG C of dryings are washed with water
Functional poly propylene non-woven fabrics.The decorative layer thickness of functional poly propylene nonwoven surface is 31nm, polypropylene before modified without
The water contact angle for spinning cloth is 133 °, and the water contact angle of functional poly propylene non-woven fabrics is 0 °, and water droplet is inhaled in 2.02s by non-woven fabrics
Receive.
Embodiment 2
0.4404g catechol is dissolved in 200mL deionized water, 0.9197g persulfuric acid is added under stirring condition
Potassium, 369 μ L dodecyl diamines are configured to reaction solution, and regulation pH value is to 8.5, then by 1.5cm × 1.5cm or so sheet glass
Immerse in above-mentioned solution, at room temperature stirring reaction 30min.After the completion of modification, sheet glass, 60 DEG C of drying functions are washed with water
Change sheet glass.The decorative layer thickness on functional glass piece surface is 35nm.
Embodiment 3
Graphene DMF/water (50: 50 (V/V)) dispersion liquid that 200mL concentration is 1mg/mL is prepared, so
0.2659g pyrogallols, 0.4564g Ammonium Persulfate 98.5s, 391 μ L diethylenetriamines are added afterwards, and regulation pH value is stirred at room temperature to 6
Reaction 50min is mixed, deionized water centrifuge washing, 60 DEG C of drying, produces functionalization graphene.The modification on functionalization graphene surface
Thickness degree is 45nm.
Embodiment 4
0.7206g caffeic acid is dissolved in 200mL deionized water, added under stirring condition 1.8394g potassium peroxydisulfates,
0.8354g polyimides is configured to reaction solution, regulation pH value to 5, then immerses 1.5cm × 1.5cm or so silicon chip above-mentioned
In solution, stirring reaction 20min at room temperature.After the completion of modification, silicon chip, 60 DEG C of drying functionalization silicon chips are washed with water.Work(
The decorative layer thickness that silicon chip surface can be changed is 32nm.
Embodiment 5
By 0.4516g3,4- dihydroxyphenyl acetic acids are dissolved in 200mL deionized water, and 0.5214g is added under stirring condition
Sodium metaperiodate, 459 μ L hexamethylene diamines are configured to reaction solution, and regulation pH value is to 3, then by 1.5cm × 1.5cm or so PVDF flat boards
Film is immersed in above-mentioned solution, at room temperature stirring reaction 40min.After the completion of modification, it is washed with water, dries produce functionalization at room temperature
PVDF Flat Membranes.The decorative layer thickness on functionalization PVDF Flat Membranes surface is 42nm.
Embodiment 6
0.7256g gallic acids are dissolved in 200mL deionized water, added under stirring condition 0.5214g Ammonium Persulfate 98.5s,
629 μ L TEPAs are configured to reaction solution, and regulation pH value is to 5, then by 1.5cm × 1.5cm or so cellulose acetate film
Immerse in above-mentioned solution, at room temperature stirring reaction 30min.After the completion of modification, it is washed with water, produces functionalization acetic acid fibre at room temperature
Tie up plain film.The decorative layer thickness on functionalization cellulose acetate film surface is 38nm.
Embodiment 7
0.7256g NSC 619661s are dissolved in 200mL alcohol water (20: 80 (V/V)) solution, added under stirring condition
3.6512g Ammonium Persulfate 98.5s, 267 μ L ethylenediamines are configured to reaction solution, and regulation pH value is to 6, then by 1.5cm × 1.5cm's or so
Polypropylene non-woven fabric is immersed in above-mentioned solution, at room temperature stirring reaction 180min.After the completion of modification, it is washed with water, 60 DEG C of drying
Produce functional poly propylene non-woven fabrics.The decorative layer thickness of functional poly propylene nonwoven surface is 105nm.
Embodiment 8
By 0.7256g3,4- dihydroxy benzenes acid ethyl acetates are dissolved in 200mL DMA/water (20: 80
(V/V) 1.8526g Ammonium Persulfate 98.5s are added) in solution, under stirring condition, 256 μ L dithioglycols are configured to reaction solution, regulation pH value
To 7, then 1.5cm × 1.5cm × 1.5cm or so melamine foams are immersed in above-mentioned solution, at room temperature stirring reaction
20min.After the completion of modification, it is washed with water, 60 DEG C of drying functionalization melamine foams.The modification on functionalization melamine foams surface
Thickness degree is 30nm.
Embodiment 9
0.7825g progallin As are dissolved in 200mL alcohol water (20: 80 (V/V)) solution, added under stirring condition
0.9128 Ammonium Persulfate 98.5,0.8356g polyimides-amine (1 generation) are configured to reaction solution, regulation pH value to 5, then by 1.5cm ×
1.5cm × 1.5cm or so melamine foams are immersed in above-mentioned solution, at room temperature stirring reaction 120min.After the completion of modification, water is used
Washing, 60 DEG C of drying functionalization melamine foams.The decorative layer thickness on functionalization melamine foams surface is 86nm.
Embodiment 10
0.8216g n butyl gallates are dissolved in 200mL alcohol water (20: 80 (V/V)) solution, added under stirring condition
Enter 1.8526g Ammonium Persulfate 98.5s, 0.4528g ends are configured to reaction solution for the dissaving polymer of amido, regulation pH value to 7, so
1.5cm × 1.5cm or so PEEK Flat Membranes are immersed in above-mentioned solution afterwards, at room temperature stirring reaction 40min.It is modified to complete
Afterwards, it is washed with water, 60 DEG C of drying functionalization PEEK Flat Membranes.The decorative layer thickness on functionalization PEEK Flat Membranes surface is
43nm。
Claims (8)
1. a kind of universal method of quick mussel bionic surface functional modification, it is characterised in that comprise the following steps：By DOPA
Amine and its derivative, oxidant and di-or higher functional reagent add mixed preparing certain pH value in solvent according to certain mol proportion
Reaction solution, then material to be finished is immersed in reaction solution, stirring at room temperature carries out surface modification, finally takes out material and washes
Wash, dry, obtain the functionalization material with certain decorative layer thickness.
2. according to claim 1, it is characterised in that：Described dopamine and its derivative be dopamine hydrochloride, catechol,
In pyrogallol, Caffeic acids, nutgall acids, 3,4- dihydroxy benzenes acids, 3,4- dihydroxy benzenes esters of gallic acid, caffeates
One or more.
3. according to claim 1, it is characterised in that：Described oxidant is one in periodate, persulfate, perchlorate
Kind.
4. according to claim 1, it is characterised in that：Described di-or higher functional reagent is binary organic amine class, polynary organic
Amine, binary mercaptan, multi-thiol, polyimides, the dendrimer that end is the dissaving polymer of amido, end is amido
One or more in class.
5. according to claim 1, it is characterised in that：Described dopamine and its derivative, oxidant and di-or higher functional examination
The mol ratio of agent is 1: 1~6: 1~10.
6. according to claim 1, it is characterised in that：Described solvent is water, ethanol, DMF, N, N- diformazans
One or more in yl acetamide.
7. according to claim 1, it is characterised in that：Described pH is allocated with NaOH and HCl, and pH value is 2~14.
8. according to claim 1, it is characterised in that：Described exterior material to be repaired is metal, nonmetallic, macromolecule, nano material
Any of.
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| CN107987578A (en) * | 2017-12-08 | 2018-05-04 | 山东交通学院 | A kind of preparation method of the surface coating products with antifouling sterilizing function |
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