CN111892633B - Tannin-epoxy silane coupling compound and preparation method thereof - Google Patents
Tannin-epoxy silane coupling compound and preparation method thereof Download PDFInfo
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Abstract
The invention provides a tannic acid-epoxy silane coupling compound and a preparation method thereof, wherein the method comprises the following steps: (1) dissolving tannic acid and tris (hydroxymethyl) aminomethane in a solvent; (2) adding gamma-glycidoxypropyltriethoxysilane (KH561) to the solution obtained in step (1); (3) and (3) heating and stirring the mixed solution obtained in the step (2) to obtain a homogeneous solution, and then refrigerating to obtain the tannin-epoxy silane coupling compound. The method has the advantages of low raw material price, simple and green preparation process, no addition of metal ions, antibacterial, antioxidant, free radical resistant and other properties of the obtained product, special fragrance similar to red wine, and good adhesion capability to skin and other materials.
Description
Technical Field
The invention belongs to the field of biomedical polymers, and relates to the field of polymer polymerization in a synthesis process, in particular to hydrolytic polycondensation of epoxy silane coupling agents and condensation reaction between polyphenol and silanol.
Background
Red wine is a well-known health drink and has the effects of reducing blood fat, inhibiting bad cholesterol, softening blood vessels, enhancing cardiovascular function and heart activity and the like. However, the red wine is not only limited to oral administration, but also can be externally used for beautifying, slowing down aging and the like, and is beneficial to the skin. The red wine has a plurality of benefits, and is due to the fact that the resveratrol, the flavonoid, the tannin and other antioxidant substances provide collagen and elastic fibers for the skin, and meanwhile, the substances can resist the damage of heavy metals and free radicals to the skin, and have potential application in the field of skin preparations.
In the components of the red wine, alcohol and antioxidant substances are indispensable and can play the roles of resisting bacteria and diminishing inflammation.
Among conventional tannin-based materials, metal-polyphenols or oxidizing agents are widely used [ Macromolecules 2017,50,666-][Chem.Mater.2019,31,5625-5632]However, metal ions (Fe)3+、Al3+) On one hand, the use of the tannin polyphenol compound can cause skin tissue damage, and on the other hand, the tannin polyphenol group has reduced oxidation resistance and free radical resistance.
Disclosure of Invention
Problems to be solved by the invention
In order to solve the technical problems, the invention provides the tannic acid-epoxy silane coupling compound which has the advantages of low raw material price, simple and green preparation process, no addition of metal ions, antibacterial, antioxidant, free radical resisting and other performances, special fragrance similar to red wine and good adhesion capability to skin and other materials, and the preparation method thereof.
Means for solving the problems
In order to solve the technical problems, the invention provides a preparation method of a tannic acid-gamma-glycidyl ether oxygen propyl triethoxy silane coupling compound, which comprises the following steps:
(1) dissolving tannic acid and tris (hydroxymethyl) aminomethane in a solvent;
(2) adding gamma-glycidyl ether oxypropyl triethoxysilane to the solution obtained in step (1);
(3) and (3) heating and stirring the mixed solution obtained in the step (2) to obtain a homogeneous solution, and then refrigerating to obtain the tannic acid-gamma-glycidyl ether oxygen propyl triethoxysilane coupling compound.
Preferably, the mass ratio of the tannic acid to the tris (hydroxymethyl) aminomethane to the solvent in the step (1) is 2-30:1: 10-50, and the solvent is C1-6Alcohol solvent or water.
Preferably, in the step (1), the mass ratio of the tannic acid to the tris (hydroxymethyl) aminomethane is 5-20:1, the solvent is water, and the dissolving temperature is room temperature to 100 ℃.
Preferably, the volume mass ratio of the gamma-glycidoxypropyltriethoxysilane to the tannic acid in the step (2) is 1-10 ml: 1g of the total weight of the composition.
Preferably, in the step (2), the gamma-glycidoxypropyltriethoxysilane is added to the solution obtained in the step (1), and then stirred vigorously.
Preferably, in the step (3), the heating temperature is 40-100 ℃, the reaction time is 0.5-5 h, and the refrigeration temperature is 0-30 ℃, and more preferably 4-room temperature.
The invention also provides a tannic acid-gamma-glycidyl ether oxygen propyl triethoxy silane coupling compound prepared by any one of the preparation methods.
Preferably, the tannic acid-gamma-glycidoxypropyltriethoxysilane coupling compound has a viscosity of 200-300 mPas.
The invention also provides the use of the above compounds in the bonding of materials, preferably glass, wood, metal, silicone rubber and plastics.
Preferably, the compound is applied to the preparation of a medicament for treating wound healing.
ADVANTAGEOUS EFFECTS OF INVENTION
(1) The tannin-epoxy silane coupling compound (TA561) has the advantages of low price of raw materials, simple and green preparation process, no addition of metal ions, antibacterial, antioxidant, free radical resistant and other properties, and has special fragrance similar to red wine.
(2) TA561 uses tannic acid as a cross-linking agent, Tris (hydroxymethyl) aminomethane (Tris) as a catalyst, and gamma-glycidoxypropyltriethoxysilane (KH561) as a silane polymer monomer, and the obtained polymer has a polyphenol functional group and an epoxy functional group, and has good adhesion to skin.
(3) The obtained polymer agent TA561 is a product of incomplete hydrolysis of silane, and has the advantages of continuous increase of molecular weight and increase of crosslinking degree along with the extension of heating time, and finally the agent is solidified or formed into a film, and has a sealing effect on skin wounds.
(4) TA561 is suitable for bonding glass, wood, metal, silicon rubber, plastic and other common materials, and can still maintain a certain adhesion force under water.
Drawings
Description of the reference numerals
FIG. 1 is a schematic diagram of the reaction process of the present invention.
FIG. 2 is a graph showing the change of viscosity of TA561 with time in example 1 of the present invention.
FIG. 3 shows the change of TA561 IR spectrum with time in example 1 of the present invention.
Fig. 4 is a graph of TA561 adhesion wood, aluminum sheet, polyvinyl chloride (PVC), Silicone Rubber (SR), and Polytetrafluoroethylene (PTFE) in example 1 of the present invention (left) and adhesion test thereof (right).
Fig. 5 is a visible-ultraviolet spectrophotometer spectrum of TA561 in situ reduction to generate gold nanoparticles (left) and silver nanoparticles (right) in example 1 of the present invention.
FIG. 6 is a transmission electron micrograph of gold nanoparticles (left) and silver nanoparticles (right) reduced by TA561 in example 1 of the present invention.
FIG. 7 is a spectrum of a UV-visible spectrophotometer of TA561 anti-1, 1-diphenyl-2-trinitrophenylhydrazine (DPPH) radical in example 1 of the present invention.
FIG. 8 shows wound healing of BALC/c mice infected with Staphylococcus aureus by TA561 of example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a tannic acid-gamma-glycidyl ether oxygen propyl triethoxy silane coupling compound, which comprises the following steps:
(1) dissolving Tannic Acid (TA) and Tris in a solvent;
(2) adding gamma-glycidoxypropyltriethoxysilane (KH561) to the solution obtained in step (1);
(3) heating and stirring the mixed solution obtained in the step (2) to obtain a homogeneous solution, and then refrigerating to obtain the tannic acid-gamma-glycidyl ether oxygen propyl triethoxysilane coupling compound, wherein the reaction process is shown in figure 1.
Wherein tannic acid is also called tanninAcid or gallotannic acid, known by the english name of Tannic acid, having the structure:
the tannin has the advantages of wide source, low cost, environmental protection, no toxicity and the like in nature, and has a large number of polyphenol groups, so the tannin also has the performances of oxidation resistance, free radical resistance, bacteria resistance, biological adhesion, heavy metal complexing and the like, and can be combined with various compounds to form macroscopic materials (gel, flocculate, polymer deposition films and the like) through covalent bond combination or supermolecule action. KH561 is an epoxy silane coupling agent, which can form a small amount of ethanol by hydrolytic polycondensation, and can dilate skin blood vessels, absorb skin moisture, and promote drug permeation; on the other hand, the linear silica polymer generated by hydrolytic polycondensation can obtain an oligomer through condensation crosslinking reaction between polyphenol and silanol to form a liquid wound healing agent, epoxy groups and polyphenol groups contained in the liquid wound healing agent can be combined with amine groups on the surface of skin, and the wound healing agent is solidified into a film along with the further increase of the condensation degree of silane, so that the wound healing agent plays a role in sealing the wound, resists the invasion of external bacteria and free radicals to the skin wound, and promotes the rapid healing of the wound.
The tannin is used as a cross-linking agent, Tris is used as a catalyst and a solubilizer, KH561 is used as a silane polymer monomer, and the obtained polymer has a polyphenol functional group and an epoxy functional group and has good adhesion capacity to skin.
The tannic acid-gamma-glycidyl ether oxypropyl triethoxysilane coupling compound is a product of incomplete silane hydrolysis, and has the advantages of continuously increased molecular weight and increased crosslinking degree along with the prolonging of heating time, and finally the preparation is solidified or formed into a film, thereby having a sealing effect on skin wounds.
The tannic acid-gamma-glycidyl ether oxygen propyl triethoxysilane coupling compound also has certain antibacterial, anti-free radical and antioxidant properties, and can be used for in-situ generation and loading of gold nanoparticles or silver nanoparticles. Meanwhile, the compound has certain divalent and trivalent metal ion complexing capacity and can effectively complexCa2+、Fe3+、Al3+、Cr3+、Zn2+、Hg2+And (4) plasma metal ions.
In a preferred embodiment, the mass ratio of the tannic acid, the tris and the solvent in the step (1) is 2-30:1: 10-50, preferably 5-20:1:15: 30; the solvent is C1-6Alcohol solvent or water of (2), wherein C1-6The alcohol solvent comprises methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol and the like, preferably, the solvent is water, more preferably deionized water, and the dissolving temperature is room temperature to 100 ℃, preferably 60 ℃.
In a preferred embodiment, the volume mass ratio of the gamma-glycidoxypropyltriethoxysilane to the tannic acid in step (2) is 1 to 10 ml: 1g, preferably 1.5-5: 1.
In a preferred embodiment, in step (2), gamma-glycidoxypropyltriethoxysilane is added to the solution obtained in step (1) and then shaken vigorously with vigorous stirring.
In a preferred embodiment, the heating temperature in step (3) is 40-100 ℃, preferably 60-85 ℃, the reaction time is 0.5-5 h, preferably 1-2h, and the refrigeration temperature is 0-30 ℃, preferably 4-room temperature.
The invention also provides the tannic acid-gamma-glycidyl ether oxygen propyl triethoxy silane coupling compound prepared by any one of the preparation methods.
In a preferred embodiment, the gamma-glycidoxypropyltriethoxysilane has a viscosity of 200-300 mPas.
The invention also provides the application of the compound in the material bonding, wherein the material is common in the field, such as glass, wood, metal, silicon rubber, plastic and the like, and the compound can still maintain certain adhesion under water.
The invention also provides application of the compound in preparing a medicament for treating wound healing. The compound releases ethanol in the early healing period of wound treatment, has certain anti-inflammatory and permeation-promoting effects, and has special fragrance similar to red wine.
The following examples may further illustrate the present invention, however, these examples should not be construed as limiting the scope of the present invention.
In the present invention, TA from Alantin reagent was used as a starting material, Tris from Sigma-Aldrich, and KH561 was commercially available from a variety of bulk reagents.
Example 1
2.0g of tannic acid and 0.20g of Tris (hydroxymethyl) aminomethane (Tris) were dissolved in 4mL of deionized water and dissolved by heating in a water bath at 60 ℃. Then 5mL of gamma-glycidoxypropyltriethoxysilane (KH561) is added into the tannin-Tris mixed solution, stirred vigorously and shaken up, stirred for 2h at 60 ℃ to obtain a homogeneous solution, and finally refrigerated at normal temperature or 4 ℃ for later use.
Example 2
3.0g of tannic acid and 0.20g of Tris were dissolved in 4mL of deionized water and dissolved by heating in a water bath at 60 ℃. Then adding 5mL KH561 into tannin-Tris mixed solution, vigorously stirring and shaking up, continuing stirring for 2h at 60 ℃ to obtain homogeneous solution, and finally refrigerating at normal temperature or 4 ℃ for later use.
Example 3
2g of tannic acid and 0.20g of Tris were dissolved in 4mL of deionized water and dissolved by heating in a water bath at 60 ℃. Then adding 10mL KH561 into tannin-Tris mixed solution, vigorously stirring and shaking up, continuing stirring for 2h at 60 ℃ to obtain homogeneous solution, and finally refrigerating at normal temperature or 4 ℃ for later use.
Example 4
3g of tannic acid and 0.20g of Tris were dissolved in 4mL of deionized water and dissolved by heating in a water bath at 60 ℃. Then adding 10mL KH561 into tannin-Tris mixed solution, vigorously stirring and shaking up, continuing stirring for 2h at 80 ℃ to obtain homogeneous solution, and finally refrigerating at normal temperature or 4 ℃ for later use.
Example 5
2.5g of tannic acid and 0.20g of Tris were dissolved in 4mL of deionized water and dissolved by heating in a water bath at 60 ℃. Then adding 7.5mL KH561 into tannin-Tris mixed solution, vigorously stirring and shaking up, continuing stirring for 1h at 85 ℃ to obtain homogeneous solution, and finally refrigerating at normal temperature or 4 ℃ for later use.
Example 6
3.0g of tannic acid and 0.20g of Tris were dissolved in 4mL of deionized water and dissolved by heating in a water bath at 60 ℃. Then adding 10mL KH561 into tannin-Tris mixed solution, vigorously stirring and shaking up, continuing stirring for 1h at 80 ℃ to obtain homogeneous solution, and finally refrigerating at normal temperature or 4 ℃ for later use.
Performance test experiment
(1) Tack test
And inserting a rotor of the viscometer into the reaction solution, maintaining the rotating speed of the rotor at 12r/min, and recording the viscosity of the reaction solution every 1 h. As shown in FIG. 2, the viscosity of the reaction solution of example 1 remained constant at the initial stage, and after 5 hours, the viscosity sharply increased and finally solidified.
(2) Infrared testing
Uniformly smearing the reaction solution on a KBr slide every 1h, volatilizing the solution until the solution is formed into a film, placing the KBr slide into an infrared spectrum tester for testing, wherein the reaction is at 995cm at the beginning of reaction as shown in figure 3-1The Si-OH characteristic peak of KH561 is rapidly disappeared, which shows that KH561 is hydrolyzed and then undergoes condensation reaction with tannin. The concentration of the reaction solution is 1079cm-1The characteristic peak of nearby Si-O-C gradually moves to 1030cm along the low frequency-1The silane undergoes polycondensation and the molecular weight increases. Therefore, the condensation reaction of KH561 and tannin self-polymerize before KH 561.
(3) Adhesion test
The samples used for the adhesion force test were 10cm in length and 2.5cm in width, and two samples were bonded by using 100. mu.L of liquid TA561 prepared in example 1, with a bonding area of 2.5 cm. times.2.5 cm, followed by hot press fixing, and the bonded samples were axially stretched by a mechanical extensometer to test the adhesion force, which can be calculated from the following formula:
where F is the tensile strength (N) at which separation of the bonded samples occurs and A is the contact area (m) between the two samples2). As shown in fig. 4, the adhesion force of TA561 to wood reaches 2.08MPa, because TA561 contains silanol and polyphenol functional groups, which respectively generate chemical bond and hydrogen bond with wood to improve the adhesion force. The bonded material is placed under water at 60 ℃ for 1h, and the bonding strength of the silicone rubber is improved, because the silanol group of TA561 can be subjected to coupling reaction with the silicon hydroxyl group on the surface of the silicone rubber under the heating condition. The above results indicate that TA561 has potential as a wearable polymeric dressing for skin preparation.
(4) In-situ preparation of noble metal nanoparticles
The solidified TA561 thin sheet (diameter 2cm, thickness 0.5cm) prepared in example 1 was immersed in HAuCl4(0.05 wt%) or AgNO3The gold nanoparticles or silver nanoparticles can be obtained by soaking in 0.1 wt% solution. As shown in fig. 5, the initial solution was colorless (dotted line in fig. 5), and the solution began to change color after 5min of immersion (dotted line in fig. 5), and the color further deepened after 10min of immersion (solid line in fig. 5), indicating that gold nanoparticles or silver nanoparticles gradually formed and increased in number. As shown in FIG. 6, the morphology is observed by a transmission electron microscope, the generated gold and silver nanoparticles are within 100nm, and TA561 loaded with noble metal nanoparticles is expected to be used for photothermal treatment of skin diseases.
(5) Anti-radical capacity test
After the solidified TA561 flake (diameter: 2cm, thickness: 0.5cm) prepared in example 1 was immersed in a 0.15mM DPPH methanol solution for 10min, the absorbance at 517nm was observed with an ultraviolet-visible spectrophotometer, and the radical trapping rate was calculated by the following formula:
wherein A iscAbsorbance at 517nm for a control DPPH solution, and AsThe absorbance of the sample group solution at 517nm was used. As shown in FIG. 7, the solid line is the control curveAnd the dotted line is the sample group curve, the DPPH free radical trapping rate of TA561 reached 94.8%. The above results indicate that DPPH has good antioxidant and anti-radical ability.
(6) Wound healing experiments
Immunocompromised male BALC/c mice (age 4-8 weeks, weight 18-22g) were used in wound healing experiments and divided into three groups (blank, KH561 and TA561 prepared in the examples of the invention), three of each. Staphylococcus aureus (concentration 3X 107CFU, 50. mu.L) was injected onto the wound surface of rats without any treatment in the blank group, while 200. mu.L of KH561 or TA561 were uniformly applied to the wound surface every 24 hours in the KH561 and TA561 groups, and the wound changes were observed by photographing. As shown in fig. 8, TA561 had the best healing effect and no obvious pus discharge compared to the blank group and KH561, indicating that TA561 acts as an ideal wound healing agent.
Claims (8)
1. A preparation method of a tannic acid-gamma-glycidyl ether oxygen propyl triethoxy silane coupling compound is characterized by comprising the following steps:
(1) dissolving tannic acid and tris (hydroxymethyl) aminomethane in a solvent;
(2) adding gamma-glycidyl ether oxypropyl triethoxysilane to the solution obtained in step (1);
(3) heating and stirring the mixed solution obtained in the step (2) to obtain a homogeneous solution, and then refrigerating to obtain the tannic acid-gamma-glycidyl ether oxypropyl triethoxysilane coupling compound;
in the step (1), the mass ratio of the tannic acid to the trihydroxymethyl aminomethane to the solvent is 2-30:1: 10-50, and the solvent is C1-6Alcohol solvent or water of (1);
in the step (2), the volume mass ratio of the gamma-glycidyl ether oxypropyl triethoxysilane to the tannic acid is 1.5-10 ml: 1g of a compound;
in the step (3), the heating temperature is 60-85 ℃, the reaction time is 0.5-5 h, and the refrigeration temperature is 0-30 ℃.
2. The method for preparing a tannic acid-gamma-glycidoxypropyltriethoxysilane coupling compound as claimed in claim 1, wherein the mass ratio of tannic acid to tris (hydroxymethyl) aminomethane in step (1) is 5-20:1, the solvent is water, and the dissolution temperature is from room temperature to 100 ℃.
3. The method for preparing a tannic acid-gamma-glycidoxypropyltriethoxysilane coupling compound as claimed in claim 1, wherein in the step (2), gamma-glycidoxypropyltriethoxysilane is added to the solution obtained in the step (1), followed by vigorous stirring and shaking.
4. The method for preparing a tannic acid- γ -glycidoxypropyltriethoxysilane coupling compound as claimed in claim 1, wherein the cooling temperature in step (3) is 4-room temperature.
5. A tannic acid-gamma-glycidoxypropyltriethoxysilane coupling compound prepared by the method of any one of claims 1 to 4.
6. The compound of claim 5, wherein the tannin- γ -glycidoxypropyltriethoxysilane coupling compound has a viscosity of 200-300 mPas.
7. Use of a compound according to claim 5 or 6 in the bonding of materials including glass, wood, metal, silicone rubber and plastics.
8. Use of a compound according to claim 5 or 6 for the manufacture of a medicament for the treatment of wound healing.
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| JP2001089868A (en) * | 1999-07-16 | 2001-04-03 | Nippon Steel Corp | Substrate treating agent for precoated metallic sheet, coated substrate treated metallic sheet coated with the same and precoated metallic sheet excellent in working adhesion of coating film using the same |
| CN1303135C (en) * | 2002-05-09 | 2007-03-07 | 杜邦唐弹性体公司 | Composition for improving adhesion of base-resistant fluoroelastomers to metal, ceramic or glass substrates |
| CN105218847A (en) * | 2015-09-14 | 2016-01-06 | 北京化工大学 | A kind of bill of material interface function method of modifying based on polyphenolic compound |
| CN109486416A (en) * | 2018-11-14 | 2019-03-19 | 哈尔滨工程大学 | A kind of oxidation film silanization treatment method |
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