Self-repairing and soluble organic silicon antibacterial elastomer, preparation method thereof and application of antibacterial material
阅读说明：本技术 一种自修复、可溶解有机硅抗菌弹性体及其制备方法与抗菌材料应用 (Self-repairing and soluble organic silicon antibacterial elastomer, preparation method thereof and application of antibacterial material ) 是由 刘月涛 张凯铭 高传慧 王传兴 武玉民 于 2020-07-27 设计创作，主要内容包括：本发明涉及一种自修复、可溶解有机硅抗菌弹性体及其制备方法与抗菌材料应用,属于柔性材料领域。本发明通过含氨基聚硅氧烷衍生物A、扩链剂含醛基单体衍生物B与3,4-二氨基呋扎C通过Schiff碱反应和与锌离子进行金属配位生成主链动态亚胺键与动态锌离子配位键的有机聚硅氧烷,制备自修复、可溶解的有机硅抗菌弹性体。本发明制备的有机硅弹性体具有良好的力学性能、溶解性能以及100℃温度下的高效自修复性能和抗菌性能,可应用于非抗生素抗菌材料、柔性抗菌材料、可拉伸抗菌材料等领域。(The invention relates to a self-repairing dissoluble organic silicon antibacterial elastomer, a preparation method thereof and application of an antibacterial material, and belongs to the field of flexible materials. According to the invention, the self-repairing soluble organosilicon antibacterial elastomer is prepared by reacting an amino-containing polysiloxane derivative A, a chain extender aldehyde-containing monomer derivative B and 3, 4-diamino furazane C through Schiff base reaction and performing metal coordination with zinc ions to generate an organopolysiloxane with a main chain dynamic imine bond and a dynamic zinc ion coordination bond. The organic silicon elastomer prepared by the invention has good mechanical property, dissolution property, high-efficiency self-repairing property and antibacterial property at the temperature of 100 ℃, and can be applied to the fields of non-antibiotic antibacterial materials, flexible antibacterial materials, stretchable antibacterial materials and the like.)
1. A self-repairing and soluble organosilicon antibacterial elastomer is characterized in that the structural formula is as follows:
wherein n is a natural number greater than zero; r1Typically methyl, phenyl or trifluoropropyl; r2Has the structural formulaWherein y is 0-10; r3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number.
2. The self-healing, dissolvable silicone antimicrobial elastomer of claim 1, wherein the molecular weight of the self-healing, dissolvable silicone antimicrobial elastomer ranges from: 3000-90000.
3. A preparation method of a self-repairing and soluble organosilicon antibacterial elastomer is characterized by comprising the following steps:
dispersing amino-containing polysiloxane derivative A, aldehyde-containing monomer derivative B and 3, 4-diamino furoxan in an organic solvent, and carrying out condensation reaction to obtain a prepolymer;
adding a solvent containing zinc ions into the prepolymer to perform a coordination reaction to obtain a self-repairing and soluble organic silicon antibacterial elastomer;
wherein the structural unit formula of the amino-containing polysiloxane derivative A is as follows:
wherein n is a natural number greater than zero; r1Typically methyl, phenyl or trifluoropropyl; r2Has the structural formulaWherein y is 0-10;
the aldehyde group-containing monomer derivative B has the following general formula:
OHC-R3-CHO
wherein R is3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number.
4. The preparation method of the self-repairing soluble organosilicon antibacterial elastomer as claimed in claim 3, wherein in the condensation reaction process, the molar content ratio of amino groups to aldehyde groups is 1-1.5: 1 to 1.5.
5. The method for preparing the self-repairing, soluble organosilicon antibacterial elastomer of claim 3, wherein the molar ratio of metal to ligand is 1: 2-32.
6. The method for preparing a self-healing, dissolvable silicone antimicrobial elastomer according to claim 3, wherein the amino-containing polysiloxane derivative A is at least one of α, ω -diaminopropyl polydimethylsiloxane, α, ω -diaminopropyl polymethylphenylsiloxane, or α, ω -diaminopropyl polymethyltrifluoropropylsiloxane.
7. The method for preparing the self-repairing and soluble organosilicon antibacterial elastomer as claimed in claim 3, wherein the molecular weight of the amino-containing polysiloxane derivative A is 1000-30000, preferably 2000-20000.
8. The method for preparing the self-repairing, dissolvable silicone antimicrobial elastomer of claim 3, wherein the aldehyde group-containing monomer derivative B chain extender is at least one of glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, or terephthalaldehyde.
9. The method for preparing the self-repairing soluble organosilicon antibacterial elastomer as claimed in claim 3, wherein the condensation reaction is carried out at 25-40 ℃ for 12-16 h.
10. Use of the self-healing, dissolvable silicone antimicrobial elastomer of any of claims 1 or 2 in the preparation of a non-antibiotic antimicrobial material, a flexible antimicrobial material, or a stretchable antimicrobial material.
Technical Field
The invention belongs to the field of flexible materials, and particularly relates to a self-repairing dissoluble organic silicon antibacterial elastomer and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the continuous development of polymer materials and antibacterial materials, the demand of various antibacterial materials in daily life of people is increasing, wherein the most prominent research field is from directions such as non-antibiotic antibacterial materials, flexible antibacterial materials, nano antibacterial materials, polymer antibacterial materials, and the like, and in order to meet the actual application requirements, the antibacterial materials are often required to have the flexibility and the stretchable ability. The organic silicon elastomer serving as an organic silicon polymer material is non-toxic and non-flammable due to excellent chemical stability and thermodynamic stability, and has excellent flexibility in a wide temperature range, so that the organic silicon elastomer is a potential raw material for preparing a flexible antibacterial material. The traditional methods of peroxide crosslinking, hydrosilylation crosslinking and the like of the organic silicon elastomer form a permanent covalent bond crosslinking network, so that the self-repairing performance is lost, and the dissolving capacity is poor. How to make the damaged silicone elastomer self-repair and recover the mechanical properties is a difficult problem. And the organic silicon elastomer prepared based on dynamic chemical bonds, such as disulfide bonds, reversible acylhydrazone, metal coordination bonds and reversible D-A reaction, can easily realize self-repair of the material through reversible damage of the dynamic chemical bonds. If research discloses a preparation method of a self-repairing organic silicon elastomer, reversible crosslinking of the organic silicon elastomer is realized by utilizing dynamic disulfide bond effect, and a self-repairing organic silicon elastomer is prepared, but the inventor finds that: the mechanical property and the degradability of the material have research space.
Disclosure of Invention
In order to overcome the problems, the invention provides a self-repairing soluble organic silicon antibacterial elastomer and a preparation method thereof. The method comprises the following steps of generating a dynamic imine bond by Schiff base reaction, forming a coordination bond between N atoms and O atoms on 1,2, 5-oxadiazole heterocycles in the 3, 4-diamino furoxan and zinc ions to realize reversible crosslinking of the organic silicon elastomer, and endowing the organic silicon elastomer with self-repairing performance by the imine bond and the zinc ion coordination bond, so that the organic silicon elastomer has excellent mechanical performance and is easily and quickly dissolved by amino and methylamino reagents; the preparation method is simple, efficient, high in practicability and easy to popularize.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a self-repairing, dissolvable silicone antimicrobial elastomer is provided, having the following structural formula:
wherein n is a natural number greater than zero; r1Typically methyl, phenyl or trifluoropropyl; r2Has the structural formula
The self-repairing and soluble organic silicon antibacterial elastomer provided by the application has good mechanical property, dissolution property, 100 ℃ self-repairing property and antibacterial property.
In a second aspect of the present invention, a method for preparing a self-repairing, dissolvable silicone antimicrobial elastomer is provided, comprising:
dispersing amino-containing polysiloxane derivative A, aldehyde-containing monomer derivative B and 3, 4-diamino furoxan in an organic solvent, and carrying out condensation reaction to obtain a prepolymer;
adding a solvent containing zinc ions into the prepolymer to perform a coordination reaction to obtain a self-repairing and soluble organic silicon antibacterial elastomer;
wherein the structural unit formula of the amino-containing polysiloxane derivative A is as follows:
wherein n is a natural number greater than zero; r1Usually methyl, phenyl orA trifluoropropyl group; r2Has the structural formula
the aldehyde group-containing monomer derivative B has the following general formula:
OHC-R3-CHO
wherein R is3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number.
The research of the invention finds that: although the organic silicon elastomer covalent bond crosslinking network prepared by peroxide crosslinking, hydrosilylation crosslinking and other modes has better mechanical property, the material is insoluble and only swells, the self-repairing performance is poor, and the preparation process is complex. Therefore, the reversible crosslinking of the organic silicon elastomer is realized by utilizing Schiff base reaction to generate dynamic imine bonds and forming coordinate bonds between N atoms and O atoms on 1,2, 5-oxadiazole heterocycles in 3, 4-diamino furoxan and zinc ions. The introduction of dynamic imine bonds can endow the polyimide film with self-repairing and dissolving properties at high temperature; the introduction of the 1,2, 5-oxadiazole heterocycle can not only form a coordinate bond with zinc ions, but also endow the material with antibacterial capability. In addition, the coordination bond of the zinc ion can enhance the self-repairing capability and the mechanical property of the material, and the mechanical property and the thermodynamic property of the material can be controlled by adjusting the molar ratio of the metal to the ligand.
The third aspect of the invention provides an application of any one of the self-repairing soluble organosilicon antibacterial elastomers in preparing non-antibiotic antibacterial materials, flexible antibacterial materials or stretchable antibacterial materials.
The organosilicon antibacterial elastomer prepared by the method has excellent mechanical property, solubility, self-repairing property and antibacterial property, so that the organosilicon antibacterial elastomer is expected to be widely applied to preparation of non-antibiotic antibacterial materials, flexible antibacterial materials or stretchable antibacterial materials.
The invention has the beneficial effects that:
(1) compared with the prior art, the method utilizes Schiff base reaction to generate dynamic imine bonds, and N atoms and O atoms on 1,2, 5-oxadiazole heterocycles in the 3, 4-diamino furo to form coordinate bond reversible crosslinking with zinc ions, and regulates the molar ratio of metal to ligand to adjust the crosslinking density, so that the compound has good mechanical property, solubility and antibacterial property.
(2) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a FT-IR plot of a silicone elastomer prepared in example 1;
FIG. 2 is an optical microscope photograph of the silicone elastomer prepared in example 1 before and after self-healing;
FIG. 3 is a stress-strain curve for silicone elastomers of example 1 prepared with different metal to ligand molar ratios;
FIG. 4 is a stress-strain curve of the silicone elastomer prepared in example 1 self-repairing at 100 ℃ for various times;
FIG. 5 is a photograph of the easy degradability process of the silicone elastomer prepared in example 1;
FIG. 6 is an antibacterial test of the silicone elastomer prepared in example 1 against E.coli;
FIG. 7 shows a silicone elastomer seed pair 10 prepared in example 12Cells/mL、103Cells/mL and 104The antibacterial efficiency of Escherichia coli in Cells/mL.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Interpretation of terms:
the term "ligand" in this application means: 3, 4-diamino furoate.
As introduced in the background art, the problems of poor mechanical property, poor dissolution property and the like still exist in the current self-repairing organic silicon elastomer material. The invention provides a self-repairing and soluble organosilicon antibacterial elastomer which comprises an amino-containing polysiloxane derivative A, a chain extender, an aldehyde-containing monomer derivative B, and 3, 4-diamino furo through condensation reaction of amino and aldehyde groups, and coordination of N atoms and O atoms on 1,2, 5-oxadiazole heterocycles in the 3, 4-diamino furo with zinc ions to form reversible dynamic imine bonds and zinc ion coordination bonds, so that the self-repairing and soluble organosilicon antibacterial elastomer is prepared.
A preparation method of a self-repairing and soluble organic silicon antibacterial elastomer comprises the steps of dispersing an amino-containing polysiloxane derivative A, an aldehyde-containing monomer derivative B and 3, 4-diamino furoxan C in an organic solvent, reacting at 25-40 ℃ for 12-16 h, adding zinc chloride dissolved in the solvent, reacting at 25-40 ℃ for 1h, and casting to obtain the self-repairing and soluble organic silicon antibacterial elastomer;
the method comprises the following specific steps:
the method comprises the following steps: dissolving amino-containing polysiloxane derivative A, chain extender aldehyde-containing monomer derivative B and 3, 4-diamino furazane C in tetrahydrofuran, fully mixing under normal pressure, heating and reacting.
Step two: dissolving zinc ions in tetrahydrofuran, adding the solution into the prepolymer, fully mixing the solution under normal pressure, heating and reacting.
Step three: and (3) heating and drying the product until the weight is constant, thus obtaining the product.
The structural unit formula of the amino-containing polysiloxane derivative A is as follows:
wherein n is a natural number greater than zero; r1Typically methyl, phenyl or trifluoropropyl; r2Has the structural formula
the general formula of the aldehyde group-containing monomer derivative B chain extender is as follows:
OHC-R3-CHO
wherein R is3Is (CH) — (CH)2)z-or a benzene ring, Z being a natural number. Such as glyoxal: OHC-CHO, malondialdehyde:
the structural formula of the 3, 4-diamino furoxan C is respectively as follows:
the research of the invention finds that: although the organic silicon elastomer covalent bond crosslinking network prepared by peroxide crosslinking, hydrosilylation crosslinking and other modes has better mechanical property, the material is insoluble and only swells, the self-repairing performance is poor, and the preparation process is complex. Therefore, the reversible crosslinking of the organic silicon elastomer is realized by utilizing Schiff base reaction to generate dynamic imine bonds and forming coordinate bonds between N atoms and O atoms on 1,2, 5-oxadiazole heterocycles in 3, 4-diamino furoxan and zinc ions. The introduction of dynamic imine bonds can endow the polyimide film with self-repairing and dissolving properties at high temperature; the introduction of the 1,2, 5-oxadiazole heterocycle can not only form a coordinate bond with zinc ions, but also endow the material with antibacterial capability. In addition, the coordination bond of the zinc ion can enhance the self-repairing capability and the mechanical property of the material, and the mechanical property and the thermodynamic property of the material can be controlled by adjusting the molar ratio of the metal to the ligand.
The invention also provides a preparation method of the self-repairing soluble organosilicon antibacterial elastomer, which is characterized in that an amino-containing polysiloxane derivative A, a chain extender, an aldehyde-containing monomer derivative B and 3, 4-diamino furo C are subjected to condensation reaction of amino and aldehyde groups, and N atoms and O atoms on 1,2, 5-oxadiazole heterocycles in the 3, 4-diamino furo are coordinated with zinc ions to form reversible dynamic imine bonds and zinc ion coordination bonds.
In order to realize the self-repairing performance of the organic silicon elastomer, aldehyde groups are introduced on amino groups blocked by an organic polysiloxane main chain, and reversible dynamic imine bonds are formed by Schiff base reaction; zinc ions are introduced into the system to form a reversible metal coordination bond, so that the self-repairing performance of the organic silicon elastomer is realized.
In some embodiments, amino-containing polysiloxane derivative a, aldehyde-containing monomer derivative B, and 3, 4-diamino furoxan are present in a molar ratio of amino to aldehyde groups of 1:1, Schiff base reaction can be effectively carried out, and complete amino and aldehyde group reaction is ensured. Furthermore, the addition of zinc ions can form metal coordinate bonds in the polymer system.
The research of the application finds that: as the metal to ligand molar ratio increases, the tensile properties, storage modulus, and glass transition temperature of the material can be improved. If the molar ratio of the metal to the ligand is too low, the effect is not significant, and if the molar ratio of the metal to the ligand is too high, precipitation may occur. For this reason, in some embodiments, the metal to ligand molar ratio is 1:32, 1:16, 1:8, 1:4, 1:2, so that the silicone elastomer has good repairing and dissolving properties, as well as good mechanical and thermodynamic properties.
The 1,2, 5-oxadiazole heterocyclic ring in the 3, 4-diamino furo has active N atom and O atom, has antibacterial capability and endows the material with high-efficiency antibacterial performance.
The structure of the amino-containing polysiloxane derivative a is not particularly limited in this application, and in some embodiments, the amino-containing polysiloxane derivative a is at least one of α, ω -diaminopropyl polydimethylsiloxane, α, ω -diaminopropyl polymethylphenylsiloxane or α, ω -diaminopropyl polymethyltrifluoropropylsiloxane, and superior self-repairing and dissolubility properties can be obtained.
In some embodiments, the molecular weight of A is 1000 to 30000, preferably 2000 to 20000.
When the silicone elastomer is synthesized, a chain extender is commonly used for carrying out a chain extension reaction on the prepolymer to increase the relative molecular mass, so in some embodiments, the chain extender containing the aldehyde group monomer derivative B is glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde or terephthalaldehyde, and the Schiff base reaction of amino and aldehyde groups is carried out to form imine bonds, so that the silicone elastomer has better thermal repair performance and solubility.
In some embodiments, the condensation polymerization of the amino and aldehyde groups is carried out at a temperature of from 25 ℃ to 40 ℃.
In some examples, studies have found that common organic synthesis reactions are employed: schiff base reaction, simple and mild reaction conditions and convenient operation.
The invention also provides polysiloxane which is prepared by any one method and has an imine bond and a zinc ion coordination bond in a main chain.
The polysiloxane with the main chain containing imine bonds and zinc ion coordination bonds can be used for preparing an organic silicon elastomer material, and has good mechanical property, solubility, self-repairing property at 100 ℃ and antibacterial property.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
In the following examples, alpha, omega-aminopropylpolysiloxanes (Mn: 2000, 3000, 5000, 10000) are commercially available polymers from: a textile material of Jiashan Jiangnan, Inc.,
the culture medium is LB culture medium, purchased from Qingdao Haibobo organism.
Other materials are also commercially available.
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