CN109180939B - Polyether sulfone with side chain containing polysulfonic acid structure and preparation method thereof - Google Patents
Polyether sulfone with side chain containing polysulfonic acid structure and preparation method thereof Download PDFInfo
- Publication number
- CN109180939B CN109180939B CN201810736406.4A CN201810736406A CN109180939B CN 109180939 B CN109180939 B CN 109180939B CN 201810736406 A CN201810736406 A CN 201810736406A CN 109180939 B CN109180939 B CN 109180939B
- Authority
- CN
- China
- Prior art keywords
- polyether sulfone
- side chain
- solution
- chain containing
- acid structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
Abstract
The invention provides polyether sulfone with a side chain containing a polysulfonic acid structure and a preparation method thereof, wherein the preparation method comprises the following steps: (1) chloromethylating polyether sulfone by using concentrated sulfuric acid and chloromethyl ether as main reagents; (2) reacting polyethylene glycol with chloromethylated polyether sulfone by using N, N-dimethylacetamide as a solvent and sodium carbonate as a catalyst; (3) using trichloromethane as a solvent, 4-dimethylaminopyridine as a catalyst and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride as a dehydrating agent to perform esterification reaction on the polyethylene glycol polyether sulfone and 4-cyano-4- (dodecyl sulfanyl thiocarbonyl) sulfanyl pentanoic acid; (4) and then adding 2-acrylamide-2-methylpropanesulfonic acid and azobisisobutyronitrile to perform RAFT polymerization reaction to prepare the polyether sulfone with a side chain containing a polysulfonic acid structure. The polyether sulfone with the side chain containing the polysulfonic acid structure, which is prepared by the invention, has good surface hydrophilicity and biocompatibility after being filmed.
Description
Technical Field
The invention relates to the field of polyether sulfone preparation, in particular to polyether sulfone with a side chain containing a polysulfonic acid structure and a preparation method thereof.
Background
In the past decades, polyethersulfone membranes have been widely accepted and widely used commercially in many fields such as water purification due to their excellent mechanical strength, film-forming properties, heat resistance and chemical resistance, and are relatively more biocompatible as blood contact materials than other materials. However, the hydrophobic property of polyethersulfone also causes some disadvantages in application, such as large membrane resistance, small flux and easy pollution caused by the hydrophobic property when used as a water treatment material, and adverse reactions such as protein adsorption, platelet adhesion and blood coagulation caused by the hydrophobic property when used as a blood contact material. Therefore, there is an urgent need to modify polyethersulfones to improve their hydrophilicity and blood compatibility.
Heparin is known to be a good anticoagulant biomolecule in blood contact materials, and many reports have been made on heparin immobilization to improve the blood compatibility of polymer materials, and the most common methods are surface modification followed by heparin immobilization, and systemic heparinization, plasma surface treatment followed by heparin deposition, and the like.
Chinese patent CN 105833748A discloses a method of heparinizing the whole polyacrylonitrile membrane by adding heparin into the membrane casting solution, chinese patent CN 105311974 a discloses a method of grafting heparin onto the polysulfone membrane with carboxylated surface, and chinese patent CN 102258946A discloses a method of depositing heparin onto the polysulfone membrane by plasma treatment; systemic heparinized membranes used in hemodialysis are prone to severe bleeding complications, the covalent binding between heparin and polymer may be broken due to the different chemical or biological environments present during the use of the heparinized material, and methods for grafting heparin onto polymeric materials often require long reaction times and rigorous procedures. The above heparin fixing methods all have some inconveniences, which limit the application of heparin-modified materials.
Therefore, methods of modifying the surface of materials by introducing functional groups such as sulfonic and carboxylic acid groups have received much attention because they can partially mimic heparin, exhibiting biological activity similar or partially similar to heparin, and these polymers mimicking the structure of heparin are called heparosan polymers.
The invention utilizes a relatively simple preparation method, effectively improves the hydrophilicity and biocompatibility of the polymer by introducing a polysulfonic acid structure and a polyethylene glycol structure into a side chain structure of a polymer molecule, and achieves the purpose of simulating the structure and function of heparin.
Disclosure of Invention
The invention aims to provide the polyether sulfone with the side chain containing the polysulfonic acid structure, which can effectively improve the hydrophilicity and the biocompatibility of a polymer after film formation and has the heparin-like function.
Polyether sulfone with side chain containing polysulfonic acid structure and structural formula of polyether sulfone
Wherein m represents the number of polyethylene glycol repeating units and is an integer of 22 to 228; n represents the number of the polyether sulfone repeating units and is an integer of 429-860; l represents the number of sulfonated structural units and is an integer of 15 to 150.
The polyether sulfone with the side chain containing the polysulfonic acid structure has the polyethylene glycol block, so that the hydrophilicity of the obtained polymer membrane is obviously improved; meanwhile, a plurality of sulfonic groups on the polymer side chain play a role in simulating heparin, and the blood compatibility and the cell compatibility of the membrane prepared from the polymer are better improved.
The invention also provides a preparation method of the polyether sulfone with the side chain containing the polysulfonic acid structure, which comprises the following steps:
(1) completely dissolving polyether sulfone powder in concentrated sulfuric acid, dropwise adding chloromethylated ether at 4-6 ℃, reacting for 3-5 hours, and processing the obtained solution to obtain chloromethylated polyether sulfone;
(2) under the protection of nitrogen, completely dissolving chloromethylated polyether sulfone and sodium carbonate obtained in the step (1) in N, N-dimethylacetamide, dropwise adding a polyethylene glycol solution dissolved in N, N-dimethylacetamide at the temperature of 65-75 ℃, reacting for 3-5 hours, and treating the obtained solution to obtain the pegylated polyether sulfone;
(3) dissolving 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in chloroform under an ice bath condition to obtain a solution A, dissolving the polyethylene glycol polyether sulfone obtained in the step (2), 4-cyano-4- (dodecyl sulfanyl thiocarbonyl) sulfanyl valeric acid and 4-dimethylaminopyridine in chloroform to obtain a solution B, dropwise adding the solution A into the solution B, heating to 30-40 ℃ after dropwise adding, reacting for 22-25 hours, and treating the obtained solution to obtain the polyethylene glycol polyether sulfone with trithiocarbonate groups;
(4) and (3) under the protection of nitrogen, completely dissolving the polyethylene glycol polyether sulfone with trithio ester groups and 2-acrylamide-2-methylpropanesulfonic acid obtained in the step (3) into N, N-dimethylacetamide, adding azobisisobutyronitrile, heating to 65-75 ℃, carrying out polymerization reaction for 22-25 hours, and treating the obtained solution to obtain the polyether sulfone with a side chain containing a polysulfonic acid structure.
The specific synthetic route of the polyether sulfone with the side chain containing the polysulfonic acid structure is as follows:
in the step (1), the mass ratio of the polyether sulfone to the concentrated sulfuric acid to the chloromethyl ether is 1: 18-19:1.6-1.7.
In the step (2), the mass ratio of the chloromethylated polyether sulfone to the sodium carbonate to the polyethylene glycol to the N, N-dimethylacetamide is 1:1:2-20: 7-60.
In the step (3), the mass ratio of 4-cyano-4- (dodecyl sulfanyl thiocarbonyl) sulfanyl pentanoic acid, 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 4-dimethylaminopyridine, polyethylene glycol polyether sulfone and trichloromethane is 1:1.2:0.3-0.4:4-25: 20-50.
In the step (4), the mass ratio of the polyethylene glycol polyether sulfone to the azodiisobutyronitrile to the 2-acrylamide-2-methylpropanesulfonic acid to the N, N-dimethylacetamide is 1:0.0015-0.01:2-3: 7.5-8.5.
Preferably, in the step (1), the particle size of the polyether sulfone powder is 1-2 μm.
In the step (1), the weight average molecular weight of the polyether sulfone powder is preferably 20000 to 250000, more preferably 100000 to 200000, and the obtained polymer has good film-forming property.
Preferably, in step (2), the molecular weight of polyethylene glycol is 1000-10000.
Compared with the prior art, the invention has the following beneficial effects:
(1) the PEG section on the polyether sulfone prepared by the invention obviously improves the hydrophilicity of the membrane, and the plurality of sulfonic groups have the function of simulating heparin, thereby better improving the blood compatibility and cell compatibility of the membrane prepared by the polymer;
(2) the covalent bond between a plurality of sulfonic acid groups on the side chain of the prepared polymer and the molecular chain of the polyether sulfone ensures that the polysulfonic acid groups carried on the prepared polyether sulfone film have good stability and are not easy to lose;
(3) the method has simple preparation process and low cost.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of polyether sulfone having a polysulfonic acid structure in a side chain obtained in example 1.
Detailed Description
Example 1
(1) Adding 180g of concentrated sulfuric acid (98%) and 10g of polyether sulfone powder with the particle size of 1.5 mu m into a three-neck round-bottom flask with a stirrer, adjusting the rotating speed of the stirrer to 800r/min, transferring the stirrer into a low-temperature cooling circulating pump after the solid is completely dissolved, dropwise adding 16g of chloromethyl ether at the temperature of 5 ℃, reacting for 4 hours, pouring the obtained solution into stirred deionized water, filtering and collecting white solid, repeatedly washing the white solid with the deionized water until the white solid is neutral, and finally placing the obtained white solid in a vacuum oven at the temperature of 80 ℃ for drying for 24 hours to obtain chloromethylated polyether sulfone;
(2) under the protection of nitrogen, placing 5g of chloromethylated polyether sulfone obtained in the step (1), 5g of sodium carbonate and 20g N, N-dimethylacetamide in a three-neck round-bottom flask with a stirrer to obtain a solution A, dissolving 10g of polyethylene glycol 1000 in 15g of N, N-dimethylacetamide to obtain a solution B, dropwise adding the solution B into the solution A at 70 ℃ for reaction for 4 hours, adding the solution obtained by the reaction into absolute ethyl alcohol which is continuously stirred, filtering and collecting white solids, repeatedly washing with deionized water, and then placing in a vacuum oven at 70 ℃ for drying for 24 hours to obtain the pegylated polyether sulfone;
(3) under the ice bath condition, dissolving 12g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in 50g of chloroform to obtain a solution A, dissolving 40g of the pegylated polyethersulfone obtained in the step (2), 10g of 4-cyano-4- (dodecylsulfanylthiocarbonyl) sulfanylvaleric acid and 3g of 4-dimethylaminopyridine in 150g of chloroform to obtain a solution B, dripping the solution A into the solution B which is continuously stirred, heating to 35 ℃ after finishing dripping, reacting for 24 hours, adding the solution obtained by the reaction into the diethyl ether which is continuously stirred, filtering and collecting a light yellow solid, repeatedly washing with the diethyl ether, and drying in a vacuum oven at 40 ℃ for 24 hours to obtain the pegylated polyethersulfone with trithio groups;
(4) adding 200g of the polyethylene glycol polyether sulfone with trithiocarbonate groups obtained in the step (3), 400g of 2-acrylamide-2-methylpropanesulfonic acid and 1500g N, N-dimethylacetamide into a three-neck round-bottom flask with a stirring device and a nitrogen introducing device, adding 2g of azobisisobutyronitrile after the solid is fully dissolved, controlling the nitrogen flow rate to be 40mL/min, introducing nitrogen for 30 minutes, heating to 70 ℃ for RAFT polymerization for 24 hours, adding the obtained reaction solution into continuously stirred diethyl ether, filtering to collect light yellow solid, repeatedly washing with diethyl ether, and drying in a vacuum oven at 40 ℃ for 24 hours to obtain the polyether sulfone with the side chain containing a polysulfonic acid structure, wherein the molecular weight of the polyether sulfone is about 1523000 by gel permeation chromatography.
The nuclear magnetism characterization of the obtained polyethersulfone with the side chain containing a polysulfonic acid structure is carried out, and the result is shown in figure 1, which shows that: the peaks at δ -8.05-8.27 correspond to the hydrogen on the benzene ring ortho to the benzyl group on the polyethersulfone backbone and the hydrogen on the nitrogen atom on the AMPS block; the peak at 7.84-8.07 corresponds to hydrogen on benzene ring at the ortho position of sulfuryl on main chain of polyethersulfone; the peak at 7.16-7.38 corresponds to hydrogen on the benzene ring meta to the sulfone group on the polyether sulfone backbone; the peak at δ -4.71-4.86 corresponds to the hydrogen of the methylene group on the benzyl group of the polyethersulfone backbone; the peaks at δ -3.51-3.72 correspond to the hydrogen of the methylene group on the polyethylene glycol block; the peaks at δ ═ 2.81 to 2.99 correspond to the hydrogen on the methylene group attached to the sulfonic acid group and the hydrogen on the methylene group attached to the trithioester group on the AMPS block; the peaks at δ ═ 2.01 to 2.25 correspond to the hydrogen on the methylene group attached to the ester group of the polyethersulfone side chain and the hydrogen of the methine of the AMPS block; the peaks at δ ═ 1.75 to 1.99 correspond to the hydrogen of the methylene group β to the ester group of the polyethersulfone side chain, the hydrogen of the methylene group on the main chain of the AMPS block, and the hydrogen of the methylene group β to the trithioester group; the peaks at δ ═ 1.29 to 1.49 correspond to the hydrogen of the methyl group on the quaternary carbon of the polyethersulfone side chain, the hydrogen of the methyl group on the AMPS block, and the hydrogen of the methylene group on the decalinear alkyl group attached to the methylene group beta to the trithioester group. Therefore, the structure of the obtained polymer was confirmed by nuclear magnetic spectrum.
Example 2
(1) Adding 190g of concentrated sulfuric acid (98%) and 10g of polyether sulfone powder with the particle size of 1.5 mu m into a three-neck round-bottom flask with a stirrer, adjusting the rotating speed of the stirrer to 800r/min, transferring the stirrer into a low-temperature cooling circulating pump after the solid is completely dissolved, dropwise adding 17g of chloromethyl ether at the temperature of 5 ℃, reacting for 4 hours, pouring the obtained solution into stirred deionized water, filtering and collecting white solid, repeatedly washing the white solid with the deionized water until the white solid is neutral, and finally placing the obtained white solid in a vacuum oven at the temperature of 80 ℃ for drying for 24 hours to obtain chloromethylated polyether sulfone;
(2) under the protection of nitrogen, placing 5g of chloromethylated polyether sulfone obtained in the step (1), 5g of sodium carbonate and 50g N, N-dimethylacetamide in a three-neck round-bottom flask with a stirrer to obtain a solution A, dissolving 100g of polyethylene glycol 10000 in 250g of N, N-dimethylacetamide to obtain a solution B, dropwise adding the solution B into the solution A at 70 ℃ for reaction for 4 hours, adding the solution obtained by the reaction into anhydrous ethanol which is continuously stirred, filtering and collecting white solids, repeatedly washing with deionized water, and then placing in a vacuum oven at 70 ℃ for drying for 24 hours to obtain the pegylated polyether sulfone;
(3) under the ice bath condition, dissolving 12g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in 100g of chloroform to obtain a solution A, dissolving 250g of the pegylated polyethersulfone obtained in the step (2), 10g of 4-cyano-4- (dodecylsulfanylthiocarbonyl) sulfanylvaleric acid and 4g of 4-dimethylaminopyridine in 150g of chloroform to obtain a solution B, dripping the solution A into the continuously stirred solution B, heating to 40 ℃ after finishing dripping, reacting for 24 hours, adding the solution obtained by the reaction into the continuously stirred diethyl ether, filtering to collect a light yellow solid, repeatedly washing with the diethyl ether, and drying in a vacuum oven at 40 ℃ for 24 hours to obtain the pegylated polyethersulfone with trithio groups;
(4) adding 200g of the polyethylene glycol polyether sulfone with trithiocarbonate groups obtained in the step (3), 600g of 2-acrylamide-2-methylpropanesulfonic acid and 1700g N, N-dimethylacetamide into a three-neck round-bottom flask with a stirring device and a nitrogen introducing device, adding 0.3g of azobisisobutyronitrile after the solid is fully dissolved, controlling the nitrogen flow rate to be 40mL/min, introducing nitrogen for 30 minutes, heating to 70 ℃ for RAFT polymerization for 24 hours, adding the obtained reaction solution into diethyl ether which is continuously stirred, filtering and collecting light yellow solid, repeatedly washing with diethyl ether, and drying in a vacuum oven at 40 ℃ for 24 hours to obtain the polyether sulfone with the side chain containing a polysulfonic acid structure, wherein the molecular weight of the polyether sulfone is about 1954000 by a gel permeation chromatography.
Example 3
(1) Adding 185g of concentrated sulfuric acid (98%) and 10g of polyether sulfone powder with the particle size of 1.5 mu m into a three-neck round-bottom flask with a stirrer, adjusting the rotating speed of the stirrer to 800r/min, transferring the stirrer into a low-temperature cooling circulating pump after the solid is completely dissolved, dropwise adding 16.5g of chloromethyl ether at the temperature of 5 ℃, reacting for 4 hours, pouring the obtained solution into stirred deionized water, filtering and collecting white solid, repeatedly washing the white solid with the deionized water until the white solid is neutral, and finally drying the obtained white solid in a vacuum oven at the temperature of 80 ℃ for 24 hours to obtain chloromethylated polyether sulfone;
(2) under the protection of nitrogen, placing 5g of chloromethylated polyether sulfone obtained in the step (1), 5g of sodium carbonate and 30g N, N-dimethylacetamide in a three-neck round-bottom flask with a stirrer to obtain a solution A, dissolving 50g of polyethylene glycol 5000 in 200g of N, N-dimethylacetamide to obtain a solution B, dropwise adding the solution B into the solution A at 70 ℃ for reaction for 4 hours, adding the solution obtained by the reaction into anhydrous ethanol which is continuously stirred, filtering and collecting white solids, repeatedly washing with deionized water, and then placing in a vacuum oven at 70 ℃ for drying for 24 hours to obtain the pegylated polyether sulfone;
(3) under the ice bath condition, 12g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride obtained in the step (2) is dissolved in 50g of trichloromethane to obtain a solution A, 150g of the polyethylene glycol polyether sulfone obtained in the step (2), 10g of 4-cyano-4- (dodecyl sulfanyl thiocarbonyl) sulfanyl pentanoic acid and 4g of 4-dimethylaminopyridine are dissolved in 300g of trichloromethane to obtain a solution B, the solution A is dripped into the solution B which is continuously stirred, the temperature is raised to 36 ℃ after the dripping is finished, the reaction is carried out for 24 hours, adding the solution obtained by the reaction into continuously stirred ether, filtering and collecting light yellow solid, repeatedly washing with the ether, and drying in a vacuum oven at the temperature of 40 ℃ for 24 hours to obtain the polyethylene glycol polyether sulfone with trithio ester groups;
(4) adding 200g of the polyethylene glycol polyether sulfone with the trithio ester group obtained in the step (3), 500g of 2-acrylamide-2-methylpropanesulfonic acid and 1600g N, N-dimethylacetamide into a three-mouth round-bottom flask with a stirring device and a nitrogen introducing device, adding 1.2g of azobisisobutyronitrile after the solid is fully dissolved, controlling the nitrogen flow rate to be 40mL/min, introducing nitrogen for 30 minutes, heating to 70 ℃ for RAFT polymerization for 24 hours, adding the obtained reaction solution into diethyl ether which is continuously stirred, filtering and collecting light yellow solid, repeatedly washing with diethyl ether, and drying in a vacuum oven at 40 ℃ for 24 hours to obtain the polyether sulfone with the side chain containing a polysulfonic acid structure, wherein the molecular weight of the polyether sulfone is about 1745000 by a gel permeation chromatography.
Example 4
(1) Adding 187g of concentrated sulfuric acid (98%) and 10g of polyether sulfone powder with the particle size of 1.5 mu m into a three-neck round-bottom flask with a stirrer, adjusting the rotating speed of the stirrer to 800r/min, transferring the stirrer into a low-temperature cooling circulating pump after the solid is completely dissolved, dropwise adding 16.7g of chloromethyl ether at the temperature of 5 ℃, reacting for 4 hours, pouring the obtained solution into stirred deionized water, filtering and collecting white solid, repeatedly washing the white solid with the deionized water until the white solid is neutral, and finally drying the obtained white solid in a vacuum oven at the temperature of 80 ℃ for 24 hours to obtain chloromethylated polyether sulfone;
(2) under the protection of nitrogen, placing 8g of chloromethylated polyether sulfone obtained in the step (1), 5g of sodium carbonate and 30g N, N-dimethylacetamide in a three-neck round-bottom flask with a stirrer to obtain a solution A, dissolving 70g of polyethylene glycol 7000 in 230g of N, N-dimethylacetamide to obtain a solution B, dropwise adding the solution B into the solution A at 70 ℃ for reaction for 4 hours, adding the solution obtained by the reaction into absolute ethyl alcohol which is continuously stirred, filtering and collecting white solids, repeatedly washing with deionized water, and then placing in a vacuum oven at 70 ℃ for drying for 24 hours to obtain the pegylated polyether sulfone;
(3) under the ice bath condition, dissolving 12g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in 50g of chloroform to obtain a solution A, dissolving 200g of the pegylated polyethersulfone obtained in the step (2), 10g of 4-cyano-4- (dodecylsulfanylthiocarbonyl) sulfanylvaleric acid and 4g of 4-dimethylaminopyridine in 400g of chloroform to obtain a solution B, dripping the solution A into the solution B which is continuously stirred, heating to 40 ℃ after finishing dripping, reacting for 24 hours, adding the solution obtained by the reaction into the diethyl ether which is continuously stirred, filtering and collecting a light yellow solid, repeatedly washing with the diethyl ether, and drying in a vacuum oven at 40 ℃ for 24 hours to obtain the pegylated polyethersulfone with trithio groups;
(4) adding 200g of the polyethylene glycol polyether sulfone with the trithio ester group obtained in the step (3), 550g of 2-acrylamide-2-methylpropanesulfonic acid and 1700g N, N-dimethylacetamide into a three-neck round-bottom flask with a stirring device and a nitrogen introducing device, adding 1.7g of azobisisobutyronitrile after the solid is fully dissolved, controlling the nitrogen flow rate to be 40mL/min, introducing nitrogen for 30 minutes, heating to 70 ℃ for RAFT polymerization for 24 hours, adding the obtained reaction solution into diethyl ether which is continuously stirred, filtering and collecting light yellow solid, repeatedly washing with diethyl ether, and drying in a vacuum oven at 40 ℃ for 24 hours to obtain the polyether sulfone with the side chain containing a polysulfonic acid structure, wherein the molecular weight of the polyether sulfone is about 1826000 by a gel permeation chromatography.
The polyether sulfone having a polysulfonic acid structure in a side chain and obtained in examples 1 to 4 and an unmodified polyether sulfone were coated on a glass plate, respectively, and a polymer membrane was obtained after film formation and was tested.
Firstly, testing the water contact angle of the polymer film by adopting a sitting drop method, and then carrying out an anticoagulation experiment on the polymer film: 0.1mL of 37 ℃ decalcified human anticoagulant plasma was added to a glass test tube coated with a polymer film, 0.1mL of 0.025mol/L calcium chloride solution was added, the tube was immersed in a 37 ℃ thermostatic water bath, a stopwatch was used to time, the time at which white filaments appeared in the tube was recorded, the measurement was repeated 5 times, and the average value was taken.
The data obtained for testing the polymer films are shown in the following table:
| water contact Angle (°) | Recalcification time(s) | |
| Unmodified | 70 | 160 |
| Example 1 | 60 | 200 |
| Example 2 | 58 | 190 |
| Example 3 | 59 | 193 |
| Example 4 | 59 | 188 |
The test result shows that: after the polyether sulfone with the side chain containing the polysulfonic acid structure is formed into a film, the water contact angle of the film is reduced, and the hydrophilicity of the film is obviously improved; meanwhile, the recalcification time of the polymer membrane obtained in the embodiment in an anticoagulation experiment is prolonged compared with that of an unmodified membrane, so that the biocompatibility of the polymer membrane is also obviously improved.
Claims (8)
1. The polyether sulfone with the side chain containing the polysulfonic acid structure is characterized in that the molecular structural formula is as follows:
wherein m is 22-228, n is 429-860, and 1 is an integer of 15-150.
2. A method for preparing the polyethersulfone with the side chain containing polysulfonic acid structure as claimed in claim 1, comprising the following steps:
(1) completely dissolving polyether sulfone powder in concentrated sulfuric acid, dropwise adding chloromethylated ether at 4-6 ℃, reacting for 3-5 hours, and processing the obtained solution to obtain chloromethylated polyether sulfone;
(2) under the protection of nitrogen, completely dissolving chloromethylated polyether sulfone and sodium carbonate obtained in the step (1) in N, N-dimethylacetamide, dropwise adding a polyethylene glycol solution dissolved in N, N-dimethylacetamide at the temperature of 65-75 ℃, reacting for 3-5 hours, and treating the obtained solution to obtain the pegylated polyether sulfone;
(3) dissolving 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in chloroform under an ice bath condition to obtain a solution A, dissolving the polyethylene glycol polyether sulfone obtained in the step (2), 4-cyano-4- (dodecyl sulfanyl thiocarbonyl) sulfanyl valeric acid and 4-dimethylaminopyridine in chloroform to obtain a solution B, dropwise adding the solution A into the solution B, heating to 30-40 ℃ after dropwise adding, reacting for 22-25 hours, and treating the obtained solution to obtain the polyethylene glycol polyether sulfone with trithiocarbonate groups;
(4) and (3) under the protection of nitrogen, completely dissolving the polyethylene glycol polyether sulfone with trithio ester groups and 2-acrylamide-2-methylpropanesulfonic acid obtained in the step (3) into N, N-dimethylacetamide, adding azobisisobutyronitrile, heating to 65-75 ℃, carrying out polymerization reaction for 22-25 hours, and treating the obtained solution to obtain the polyether sulfone with a side chain containing a polysulfonic acid structure.
3. The method for preparing the polyether sulfone having the side chain containing the polysulfonic acid structure as claimed in claim 2, wherein in the step (1), the mass ratio of the polyether sulfone to the concentrated sulfuric acid to the chloromethyl ether is 1: 18 to 19:1.6 to 1.7.
4. The method for preparing polyether sulfone having a side chain containing a polysulfonic acid structure as claimed in claim 2, wherein in step (2), the mass ratio of chloromethylated polyether sulfone, sodium carbonate, polyethylene glycol and N, N-dimethylacetamide is 1:2-20: 7-60.
5. The method for preparing polyether sulfone having a side chain containing a polysulfonic acid structure as claimed in claim 2, wherein in the step (3), the mass ratio of 4-cyano-4- (dodecylsulfanylthiocarbonyl) sulfanylpentanoic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4-dimethylaminopyridine, pegylated polyether sulfone and chloroform is 1:1.2:0.3-0.4:4-25: 20-50.
6. The method for preparing polyether sulfone having a side chain containing a polysulfonic acid structure as claimed in claim 2, wherein in step (4), the mass ratio of the pegylated polyether sulfone, azobisisobutyronitrile, 2-acrylamido-2-methylpropanesulfonic acid, and N, N-dimethylacetamide is 1:0.0015-0.01:2-3: 7.5-8.5.
7. The method for preparing the polyether sulfone containing the polysulfonic acid structures on the side chains as claimed in claim 2, wherein in the step (1), the particle size of the polyether sulfone powder is 1-2 μm.
8. The method for preparing polyether sulfone having a polysulfonic acid structure in its side chain as claimed in claim 2, wherein in step (1), said polyether sulfone powder has a weight-average molecular weight of 20000-250000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810736406.4A CN109180939B (en) | 2018-07-06 | 2018-07-06 | Polyether sulfone with side chain containing polysulfonic acid structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810736406.4A CN109180939B (en) | 2018-07-06 | 2018-07-06 | Polyether sulfone with side chain containing polysulfonic acid structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109180939A CN109180939A (en) | 2019-01-11 |
| CN109180939B true CN109180939B (en) | 2021-03-09 |
Family
ID=64936179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810736406.4A Active CN109180939B (en) | 2018-07-06 | 2018-07-06 | Polyether sulfone with side chain containing polysulfonic acid structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109180939B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116589681B (en) * | 2023-07-17 | 2023-09-12 | 富海(东营)新材料科技有限公司 | Sulfonated polyether sulfone as well as preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2738358A1 (en) * | 2008-09-29 | 2010-04-01 | Richard T. Zvosec | Process for accelerated capture of carbon dioxide |
| CN103193941A (en) * | 2013-04-03 | 2013-07-10 | 浙江大学 | Polyether sulfone copolymer modified by sulphobetaine metacrylic acid ester as well as preparation method and application of polyether sulfone copolymer |
| CN103301759A (en) * | 2013-06-22 | 2013-09-18 | 威海威高血液净化制品有限公司 | Polysulfone hollow fiber dialysis membrane and preparation method thereof |
| CN103877873A (en) * | 2014-03-14 | 2014-06-25 | 西北大学 | Preparation method of anti-pollution hydrophilic polysulfone membrane modified by amphiphilic amino acid |
| CN104984664A (en) * | 2015-06-20 | 2015-10-21 | 杭州汉膜新材料科技有限公司 | Method for preparing amino acid modified polyether sulfone hematodialysis membrane |
| CN105311974A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院大连化学物理研究所 | Blood dialysis membrane with high blood coagulation resistance and preparation method therefor |
| CN105669912A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Method for preparing star polycarboxylate water reducing agent |
| CN105713154A (en) * | 2015-12-11 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Preparation method of early-strength polycarboxylic acid water reducer |
| CN106943901A (en) * | 2017-05-12 | 2017-07-14 | 中南大学 | Biocompatibility PS membrane that sulfonation hydroxypropyl chitosan is modified and preparation method thereof |
-
2018
- 2018-07-06 CN CN201810736406.4A patent/CN109180939B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2738358A1 (en) * | 2008-09-29 | 2010-04-01 | Richard T. Zvosec | Process for accelerated capture of carbon dioxide |
| CN103193941A (en) * | 2013-04-03 | 2013-07-10 | 浙江大学 | Polyether sulfone copolymer modified by sulphobetaine metacrylic acid ester as well as preparation method and application of polyether sulfone copolymer |
| CN103301759A (en) * | 2013-06-22 | 2013-09-18 | 威海威高血液净化制品有限公司 | Polysulfone hollow fiber dialysis membrane and preparation method thereof |
| CN103877873A (en) * | 2014-03-14 | 2014-06-25 | 西北大学 | Preparation method of anti-pollution hydrophilic polysulfone membrane modified by amphiphilic amino acid |
| CN105311974A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院大连化学物理研究所 | Blood dialysis membrane with high blood coagulation resistance and preparation method therefor |
| CN104984664A (en) * | 2015-06-20 | 2015-10-21 | 杭州汉膜新材料科技有限公司 | Method for preparing amino acid modified polyether sulfone hematodialysis membrane |
| CN105713154A (en) * | 2015-12-11 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Preparation method of early-strength polycarboxylic acid water reducer |
| CN105669912A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Method for preparing star polycarboxylate water reducing agent |
| CN106943901A (en) * | 2017-05-12 | 2017-07-14 | 中南大学 | Biocompatibility PS membrane that sulfonation hydroxypropyl chitosan is modified and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109180939A (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Direct synthesis of heparin-like poly (ether sulfone) polymer and its blood compatibility | |
| Park et al. | Polysulfone-graft-poly (ethylene glycol) graft copolymers for surface modification of polysulfone membranes | |
| Ma et al. | Toward highly blood compatible hemodialysis membranes via blending with heparin-mimicking polyurethane: Study in vitro and in vivo | |
| KR20030032025A (en) | Graft copolymers, methods for grafting hydrophilic chains onto hydrophobic polymers, and articles thereof | |
| CN100384521C (en) | Method for improving hydrophilicity of polymer porous membrane by dentritic branching molecule | |
| CN109663510B (en) | Zwitterionic random copolymer P (MMA)x-r-CBMAy) Modified PVDF antifouling film and preparation method thereof | |
| JPH06254158A (en) | Diaphragm and its preparation | |
| WO2000011058A1 (en) | Highly branched block copolymers | |
| Yan et al. | Graft copolymerization of 2‐methacryloyloxyethyl phosphorylcholine to cellulose in homogeneous media using atom transfer radical polymerization for providing new hemocompatible coating materials | |
| CN109180939B (en) | Polyether sulfone with side chain containing polysulfonic acid structure and preparation method thereof | |
| US4118439A (en) | Polyelectrolytes | |
| Niu et al. | Modification of a polyethersulfone membrane with a block copolymer brush of poly (2-methacryloyloxyethyl phosphorylcholine-co-glycidyl methacrylate) and a branched polypeptide chain of Arg–Glu–Asp–Val | |
| CA2133955C (en) | Polyetheramidoamine hydrogels as heparinizable materials | |
| CN115260504B (en) | Zwitterionic-containing polyarylethersulfone block copolymer, anti-pollution ultrafiltration membrane, preparation method and application | |
| Li et al. | One‐pot synthesized poly (vinyl pyrrolidone‐co‐methyl methacrylate‐co‐acrylic acid) blended with poly (ether sulfone) to prepare blood‐compatible membranes | |
| Ran et al. | Bionic design for anticoagulant surface via synthesized biological macromolecules with heparin-like chains | |
| JPH10501565A (en) | Azlactone-functional membranes and methods of making and using same | |
| JP3948993B2 (en) | Polysulfone copolymer | |
| TWI583708B (en) | Polymer and method for preparing the same | |
| FI89502C (en) | THE FRAMEWORK OF THE POLYMER OF THE SWIMMING PLATE AND OF THE FRAMEWORK | |
| TWI579333B (en) | Ion exchange membrane | |
| JP2006124714A (en) | Contamination resistant material and contamination resistant semipermeable membrane | |
| WO2024018999A1 (en) | Polymer compound | |
| JP3690019B2 (en) | Aromatic polysulfone polymer and process for producing the same | |
| EP0860199B1 (en) | Method of producing a membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |