CN109021229B - Preparation method and application of sulfur-containing hyperbranched polyglycidyl ether copolymer - Google Patents
Preparation method and application of sulfur-containing hyperbranched polyglycidyl ether copolymer Download PDFInfo
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- C08J2381/06—Polysulfones; Polyethersulfones
Abstract
The invention discloses a preparation method and application of a sulfur-containing hyperbranched polyglycidyl ether copolymer, and belongs to the technical field of biological medicines. Under the action of strong base and 1,1, 1-trimethylolethane monomer, carrying out random copolymerization on glycidol and glycidol alkene/propargyl ether through anion ring-opening polymerization to obtain hyperbranched poly (glycidol-random-glycidol allyl ether), and carrying out click reaction on the hyperbranched poly (glycidol-random-glycidol allyl ether-click-aminoethanethiol) and thiol compounds under the action of photoinitiator and ultraviolet light to obtain hyperbranched poly (glycidol-random-glycidol allyl ether-click-aminoethanethiol), namely, a sulfur-containing hyperbranched polyglycidyl ether copolymer. The method has the advantages of simple and easily obtained comonomers, convenient synthesis of the random copolymer, mild conditions, simple reaction steps, easy realization and great reduction of the cost. The permeable membrane modified by the copolymer has a large number of hydroxyl functional end groups on the surface, is easy to perform subsequent functionalization, and is suitable for the field of biomedicine.
Description
Technical Field
The invention belongs to the technical field of biological medicines, and particularly relates to a preparation method and application of a sulfur-containing hyperbranched polyglycidyl ether copolymer.
Technical Field
In recent years, because of their many outstanding advantages in biomedical technology, etc., polyglycidyl ethers have received increasing attention from researchers. The polymer has the advantages of simple and easily obtained raw materials, low price, no biotoxicity and wide application prospect in the aspect of biomedicine. In addition, the polyglycidyl ether material can play a role in reducing pollution accumulation due to lower surface adsorption performance in water, so that the surface pollution is well reduced, and the service life of the material is prolonged.
The hyperbranched polyglycidyl ether copolymer has a dendritic hyperbranched structure, is used as a modified coating, is more favorable for protecting the surface of an object, increases the hydrophilicity, and shows a good anti-pollution enhancement effect. A hyperbranched polyglycidyl ether modified polyamide composite membrane was first reported in Li equalling 2014 and applied to pressure retarded osmosis power generation (Li X.et.Environ.Sci.Technol.2014, 48, 9898-. Li et al also performed water treatment cleaning studies on surface charged hyperbranched polyglycidyl ether modified pressure retarded osmosis membranes to enhance their applicability in sewage (Li X.et. J.Membr.Sci.2017,522, 116-123.).
The sulfur-containing compound can be coupled with silver ions, can improve the antibacterial capacity of the compound, and is widely applied to the fields of chemical industry, medicine and the like. The current report about the sulfur-containing hyperbranched polyglycidyl ether modified membrane is limited to the application research of a single glycidyl polymer in pressure retardation permeation (Zhang Y.et al.J.Membr.Sci.2018,563,521-530.), and the polymer has a single polymerization structure, is complex in preparation method steps, needs more energy consumption and is not suitable for being applied to the field of biological medicine.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method and application of a sulfur-containing hyperbranched polyglycidyl ether copolymer.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a sulfur-containing hyperbranched polyglycidyl ether copolymer comprises the following steps:
(1) under the action of strong base (catalyst) and 1,1, 1-trimethylolethane monomer (initiator), carrying out random copolymerization by anion ring-opening polymerization to obtain hyperbranched poly (glycidyl-random-glycidyl alkene/propargyl ether). Wherein the molar ratio of the glycidol to the glycidol allyl ether or the glycidol propargyl ether is preferably 1: 99-99: 1; the strong base is preferably one of sodium methoxide, potassium tert-butoxide, cesium hydroxide or sodium hydride.
(2) Under the action of a photoinitiator and ultraviolet light, a thiol compound and hyperbranched poly (glycidyl-random-glycidyl ene/propargyl ether) are subjected to click reaction to obtain hyperbranched poly (glycidyl-random-glycidyl ene/propargyl ether-click-aminoethanethiol), namely the sulfur-containing hyperbranched polyglycidyl ether copolymer. The photoinitiator is preferably 2, 2-dimethoxy-2-phenylacetophenone (DMPA), and the molar ratio of the photoinitiator to the alkene/propargyl in the hyperbranched poly (glycidol-random-glycidol alkene/propargyl ether) is preferably 1: 2-1: 10; the thiol compound is preferably 2-aminoethanethiol or SH-R1-NH2，R1Is (CH)2)n，n>And 2, the molar ratio of the compound to the hyperbranched poly (glycidol-random-glycidol alkene/propargyl ether) is preferably 2:1 to 5: 1.
The chemical reaction formula of the step (1) is as follows:
the chemical reaction formula of the step (2) is as follows:
a sulfur-containing hyperbranched polyglycidyl ether copolymer, which is prepared by the method.
The application of the sulfur-containing hyperbranched polyglycidyl ether copolymer in modifying permeable membranes.
The method for modifying the permeable membrane by the sulfur-containing hyperbranched polyglycidyl ether copolymer comprises the following steps:
(1) the sulfur-containing hyperbranched polyglycidyl ether copolymer is grafted and modified on the permeable membrane.
(2) Soaking the permeable membrane modified by the sulfur-containing hyperbranched polyglycidyl ether copolymer into a silver ion solution to couple silver ions into the modification layer. The silver ion solution is preferably silver nitrate solution or silver acetate solution.
Preferably, step (1) of the above method for modifying a permeable membrane comprises the steps of:
1) dissolving dopamine hydrochloride in 0.01mol L-1、8.0<pH<Preparing solution A in Tris buffer solution of 8.6, and immersing the permeable membrane into the solution A to fully coat the dopamine hydrochloride on the permeable membrane (8-12 h). Wherein the concentration of the dopamine hydrochloride in the solution A is preferably 100-500 mg/L.
2) And adding triethylamine into the aqueous solution of the sulfur-containing hyperbranched polyglycidyl ether copolymer to prepare a solution B, and then immersing the permeable membrane coated with dopamine hydrochloride into the solution B for 0.5-6 h. The concentration of the sulfur-containing hyperbranched polyglycidyl ether copolymer in the solution B is preferably 10-100 g/L, and the volume fraction of triethylamine in the solution B is preferably 0.2-0.7%.
The permeable membrane is preferably a membrane made of polyethersulfone, polysulfone, polyamide, polyacrylonitrile, polyvinylidene fluoride, or cellulose acetate.
A sulfur-containing hyperbranched polyglycidyl ether copolymer modified permeable membrane is prepared by the method.
The permeable membrane modified by the sulfur-containing hyperbranched polyglycidyl ether copolymer can be used in different fields, such as biological medicines and the like.
The sulfur-containing hyperbranched polyglycidyl ether copolymer prepared by the method can be obtained by reacting in an aqueous solution at normal temperature, the reaction steps are simple, and the yield is over 75 percent; the prepared permeable membrane modified by the sulfur-containing hyperbranched polyglycidyl ether copolymer has hydrophilic surface, a large number of hydroxyl functional end groups, easy subsequent functionalization, no biotoxicity and good biocompatibility, and is very suitable for being applied to the field of biological medicines.
The method has the beneficial effects that:
(1) the comonomer used in the invention is simple and easy to obtain, the random copolymer is convenient to synthesize, the condition is mild, and the implementation is easy;
(2) the raw materials used in the invention have low price, and the copolymerization reaction is convenient for introducing other functional groups which can be used for subsequent reaction and is easy to amplify.
(3) The ultraviolet light is used for initiating the sulfydryl-alkenyl and sulfydryl-alkynyl click reaction, the selectivity is good, the reaction time is short (<1h), the click efficiency is high (> 99%), the obtained amino end group is easy to store and difficult to oxidize, the introduction of sulfur element can be used for subsequent coupling of silver ions, the antibacterial capability of the modification layer is further improved, and the self-repairing function of the modification layer is easily endowed.
Drawings
FIG. 1 is a fluorescent adsorption test chart of unmodified membrane (a), hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified membrane (b) bovine serum albumin;
FIG. 2 is a graph of gram-negative E.coli adsorption assays for unmodified membrane (a), hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified membrane (b);
FIG. 3 is a graph of gram-positive Staphylococcus aureus adsorption tests of an unmodified membrane (a), a hyperbranched poly (glycidol-random-glycidol allyl ether-click-aminoethanethiol) modified membrane (b).
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples for the purpose of facilitating understanding and practice of the invention by those of ordinary skill in the art, and it is to be understood that the present invention has been described in the illustrative embodiments and is not to be construed as limited thereto.
Example 1
24.3mg of sodium methoxide and 181mg of 1,1, 1-trimethylolethane were added to 2.0mL of methanol, and the mixture was reacted at 60 ℃ for 2 hours, dried overnight in a vacuum oven at 80 ℃ to remove all the solvent, and the solid was dispersed in 40mL of 1, 4-dioxane. Mixing 8.0mL of glycidol, 3.6mL of glycidol allyl ether and 10mL of 1, 4-dioxane, introducing argon to remove oxygen in the mixed solution, slowly dripping the mixed solution into the dispersion liquid within 12h at the reaction temperature of 100 ℃, continuing the reaction for 6h after finishing dripping, and polymerizing to obtain the hyperbranched poly (glycidol-random-glycidol allyl ether). After the reaction is finished, the mixture is precipitated in n-hexane, and the polymer is purified by repeatedly dissolving the mixture in methanol and precipitating the mixture in n-hexane to obtain white viscous hyperbranched poly (glycidol-random-glycidol allyl ether) with the molecular weight of 6300 g/mol.
Dissolving 1.26g of hyperbranched poly (glycidyl-random-glycidyl allyl ether) with the molecular weight of 6300g/mol in 10mL of N, N-dimethylformamide, adding 0.46g of 2-aminoethanethiol and 77mg of 2, 2-dimethoxy-2-phenylacetophenone, uniformly mixing, and reacting for 1h under 365nm ultraviolet light to obtain a hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) solution. After the reaction is finished, the mixture is precipitated in n-hexane, and the polymer is purified by repeatedly dissolving the mixture in methanol and precipitating the mixture in n-hexane to obtain white viscous hyperbranched poly (glycidol-random-glycidol allyl ether-click-aminoethanethiol) with the molecular weight of 7500 g/mol.
Example 2
24.3mg of sodium methoxide and 181mg of 1,1, 1-trimethylolethane were added to 2.0mL of methanol, and the mixture was reacted at 60 ℃ for 2 hours, dried overnight in a vacuum oven at 80 ℃ to remove all the solvent, and the solid was dispersed in 40mL of 1, 4-dioxane. Mixing 2.0mL of glycidol, 14.4mL of glycidol allyl ether and 10mL of 1, 4-dioxane, introducing argon to remove oxygen in the mixed solution, slowly dripping the mixed solution into the dispersion liquid within 12h at the reaction temperature of 100 ℃, continuing the reaction for 6h after finishing dripping, and polymerizing to obtain the hyperbranched poly (glycidol-random-glycidol allyl ether). After the reaction is finished, the mixture is precipitated in n-hexane, and the polymer is purified by repeatedly dissolving the mixture in methanol and precipitating the mixture in n-hexane to obtain white viscous hyperbranched poly (glycidol-random-glycidol allyl ether), wherein the molecular weight of the hyperbranched poly (glycidol-random-glycidol allyl ether) is 8100 g/mol.
Dissolving 1.62g of hyperbranched poly (glycidyl-random-glycidyl allyl ether) with the molecular weight of 8100g/mol in 10mL of N, N-dimethylformamide, adding 1.85g of 2-aminoethanethiol and 307mg of 2, 2-dimethoxy-2-phenylacetophenone, uniformly mixing, and reacting for 1h under 365nm ultraviolet light to obtain a hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) solution. After the reaction is finished, the mixture is precipitated in n-hexane, and the polymer is purified by repeatedly dissolving the mixture in methanol and precipitating the mixture in n-hexane to obtain white viscous hyperbranched poly (glycidol-random-glycidol allyl ether-click-aminoethanethiol) with the molecular weight of 12700 g/mol.
Example 3
24.3mg of sodium methoxide and 181mg of 1,1, 1-trimethylolethane were added to 2.0mL of methanol, and the mixture was reacted at 60 ℃ for 2 hours, dried overnight in a vacuum oven at 80 ℃ to remove all the solvent, and the solid was dispersed in 40mL of 1, 4-dioxane. Mixing 6.0mL of glycidol, 6.50mL of glycidol propargyl ether and 10mL of 1, 4-dioxane, introducing argon to remove oxygen in the mixed solution, slowly dripping the mixed solution into the dispersion liquid within 12h at the reaction temperature of 100 ℃, continuing the reaction for 6h after finishing dripping, and polymerizing to obtain the hyperbranched poly (glycidol-random-glycidol propargyl ether). After the reaction is finished, the mixture is precipitated in n-hexane, and the polymer is purified by repeatedly dissolving in methanol and precipitating in n-hexane to obtain white viscous hyperbranched poly (glycidol-random-glycidol propargyl ether) with the molecular weight of 6800 g/mol.
Dissolving 1.36g of hyperbranched poly (glycidol-random-glycidol propargyl ether) with the molecular weight of 6800g/mol in 10mL of N, N-dimethylformamide, adding 1.83g of 2-aminoethanethiol and 153mg of 2, 2-dimethoxy-2-phenylacetophenone, uniformly mixing, and reacting for 1h under 365nm ultraviolet light to obtain a hyperbranched poly (glycidol-random-glycidol propargyl ether-click-aminoethanethiol) solution. After the reaction is finished, the mixture is precipitated in n-hexane, and the polymer is purified by repeatedly dissolving the mixture in methanol and precipitating the mixture in n-hexane, so that white viscous hyperbranched poly (glycidol-random-glycidol propargyl ether-click-aminoethanethiol) with the molecular weight of 11500g/mol is obtained.
Example 4
Dopamine solution was prepared by dissolving 100mg of dopamine hydrochloride in 1L0.01mol/L, pH ═ 8.0 Tris buffer. And (3) immersing the permeable membrane into a dopamine solution for 12 hours, and washing the immersed permeable membrane for 3 times by using deionized water to prepare the dopamine-coated permeable membrane. The permeable membrane is made of polyethersulfone, polysulfone, polyamide, polyacrylonitrile, polyvinylidene fluoride or cellulose acetate.
The 7500g/mol hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) prepared in example 1 was prepared as a 50g/L aqueous solution, and triethylamine was added thereto to a final concentration of 0.7% (volume fraction) and stirred uniformly. The dopamine coated permeable membrane was immersed in a hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) solution for 6 hours. And then immersing the permeable membrane into 0.1g/L silver nitrate water solution for 6 hours to obtain the hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified membrane.
Example 5
In this example, the unmodified membrane was a polyethersulfone membrane which had not been subjected to any treatment, and the modified membrane was a polyethersulfone membrane treated in the same manner as in example 4.
As shown in FIGS. 1a and 1b, bovine serum albumin fluorescence adsorption test charts of an unmodified membrane and a hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified membrane are shown, wherein the unmodified membrane and the hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified membrane are rinsed with 10mmol/L phosphate buffer solution for 2 times, and immersed in a phosphate buffered saline solution of fluorescently labeled bovine serum albumin (0.5mg/L) for 1 hour at room temperature. Fluorescence measurements were performed using a Leica DMLM fluorescence spectrometer. FIGS. 1a and 1b show the results of fluorescence measurement, respectively. The unmodified membrane surface is completely covered by protein, i.e. the unmodified membrane is subject to severe protein adhesion, see fig. 1 a. The surface of the membrane modified by the copolymer has only weak fluorescence, which shows that only a small amount of adhesion exists. As can be seen from the adhesion strength, the hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified film adhesion strength decreased from 92% to 8%, see fig. 1 b.
Example 6
In this example, the unmodified membrane was a polyethersulfone membrane which had not been subjected to any treatment, and the modified membrane was a polyethersulfone membrane treated in the same manner as in example 4.
As shown in fig. 2a and 2b, respectively, are gram-negative escherichia coli adsorption test charts of an unmodified membrane and a hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified membrane; the unmodified membrane and the hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified membrane are respectively rinsed with 10mmol/L phosphate buffer solution for 2 times, and immersed in phosphate buffer solution containing Escherichia coli (1 × 10)8Total bacterial population per ml) for 4 hours, and determined by scanning electron microscopy, and fig. 2a and 2b are the results of the scanning electron microscopy. The unmodified membrane surface is densely covered by escherichia coli and even has bacterial clusters, and only sporadic escherichia coli adheres to the membrane surface after the modification of the copolymer as shown in figure 2 a. From the quantitative determination of the adhesion strength, it can be seen that the hyperbranched poly (glycidol-random-glycidol allyl ether-click-aminoethanethiol) adhesion strength decreases from 100% to 8.1%, see fig. 2 b.
Example 7
In this example, the unmodified membrane was a polyethersulfone membrane which had not been subjected to any treatment, and the modified membrane was a polyethersulfone membrane treated in the same manner as in example 4.
FIG. 3a and FIG. 3b show the gram-positive membrane of unmodified membrane and hyperbranched poly (glycidol-random-glycidol allyl ether-click-aminoethanethiol) modified membraneThe staphylococcus aureus adsorption test chart is that an unmodified membrane and a hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified membrane are respectively rinsed with 10mmol/L phosphate buffer solution for 2 times and soaked in a phosphate buffer solution (1 multiplied by 10) containing staphylococcus aureus at room temperature8Total bacterial population per ml) for 4 hours, and determined by scanning electron microscopy, and fig. 3a and 3b are the results of the scanning electron microscopy. The unmodified membrane surface is densely covered by bacteria and has a large number of bacterial clusters, as shown in figure 3a, and only a small amount of bacteria are adhered to the membrane surface after the modification of the copolymer. From the quantitative determination of the adhesion strength, it can be seen that the hyperbranched poly (glycidyl-random-glycidyl allyl ether-click-aminoethanethiol) modified film adhesion strength decreases from 100% to 9.2%, see fig. 3 b.
It should be understood that parts of the specification not set forth in detail are well within the prior art.
It should be understood that the above description of the preferred embodiments is given for clearness of understanding and no unnecessary limitations are to be understood therefrom, for those skilled in the art may make modifications and alterations within the scope of the invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a sulfur-containing hyperbranched polyglycidyl ether copolymer is characterized by comprising the following steps: the method comprises the following steps:
(1) under the action of strong base and 1,1, 1-trimethylolethane monomer, carrying out random copolymerization on glycidol and glycidol allyl ether or glycidol propargyl ether through anion ring-opening polymerization to obtain hyperbranched poly (glycidol-random-glycidol alkene/propargyl ether);
(2) under the action of a photoinitiator and ultraviolet light, carrying out click reaction on an aminothiol compound and hyperbranched poly (glycidol-random-glycidol alkene/propargyl ether) to obtain hyperbranched poly (glycidol-random-glycidol alkene/propargyl ether-click-aminothiol); said aminothiol compoundThe compound is 2-aminoethanethiol or SH-R1-NH2，R1Is (CH)2)n，n>2。
2. The method of claim 1, wherein: in the step (1), the molar ratio of glycidol to glycidol allyl ether or glycidol propargyl ether is 1: 99-99: 1; the strong base is one of sodium methoxide, potassium tert-butoxide, cesium hydroxide or sodium hydride.
3. The method of claim 1, wherein: in the step (2), the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone, and the molar ratio of the photoinitiator to alkene/propargyl in the hyperbranched poly (glycidol-random-glycidol alkene/propargyl ether) is 1: 2-1: 10;
the molar ratio of the aminothiol compound to the hyperbranched poly (glycidol-random-glycidol alkene/propargyl ether) is 2: 1-5: 1.
4. A sulfur-containing hyperbranched polyglycidyl ether copolymer is characterized in that: prepared by the process of any one of claims 1 to 3.
5. Use of the sulfur-containing hyperbranched polyglycidyl ether copolymer of claim 4 for modifying permeable membranes.
6. The method for modifying permeable membranes according to claim 4, wherein the method comprises the following steps: the method comprises the following steps:
(1) grafting and modifying sulfur-containing hyperbranched polyglycidyl ether copolymer on a permeable membrane;
(2) soaking the permeable membrane modified by the sulfur-containing hyperbranched polyglycidyl ether copolymer into a silver ion solution to couple silver ions into the modification layer.
7. The method of claim 6, wherein: the step (1) comprises the following steps:
1) dissolving dopamine hydrochloride in 0.01mol L-1、8.0<pH<8.6, preparing a solution A in a Tris buffer solution, and immersing the permeable membrane into the solution A to fully coat dopamine hydrochloride on the permeable membrane;
2) and adding triethylamine into the aqueous solution of the sulfur-containing hyperbranched polyglycidyl ether copolymer to prepare a solution B, and then immersing the permeable membrane coated with dopamine hydrochloride into the solution B for 0.5-6 h.
8. Use according to claim 5, characterized in that: the permeable membrane is made of polyethersulfone, polysulfone, polyamide, polyacrylonitrile, polyvinylidene fluoride or cellulose acetate.
9. The method according to claim 6 or 7, characterized in that: the permeable membrane is made of polyethersulfone, polysulfone, polyamide, polyacrylonitrile, polyvinylidene fluoride or cellulose acetate.
10. A permeable membrane modified by sulfur-containing hyperbranched polyglycidyl ether copolymer, which is characterized in that: prepared by the process of claim 6 or 7.
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