CN109180939A - A kind of polyether sulfone and preparation method thereof of the side chain containing more Sulfonic acid structures - Google Patents
A kind of polyether sulfone and preparation method thereof of the side chain containing more Sulfonic acid structures Download PDFInfo
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Abstract
A kind of polyether sulfone and preparation method thereof the present invention provides side chain containing more Sulfonic acid structures includes the following steps: (1) using the concentrated sulfuric acid, chloromethyl ether as main agents, carries out chloromethylation processing to polyether sulfone；(2) with N, N- dimethyl amine is solvent, and sodium carbonate is catalyst, reacts polyethylene glycol with chloromethylation polyether sulfone；(3) solvent is done with chloroform, 4-dimethylaminopyridine is catalyst, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is dehydrating agent, makes Pegylation polyether sulfone and 4- cyano -4- (dodecyl sulfanyl thiocarbonyl) sulfanyl valeric acid that esterification occur；(4) 2- acrylamide-2-methyl propane sulfonic and azodiisobutyronitrile are added, RAFT polymerization reaction is carried out, polyether sulfone of the side chain containing more Sulfonic acid structures is made.The side chain that the present invention is prepared has good surface hydrophilicity and biocompatibility after the polyether sulfone film forming containing more Sulfonic acid structures.
Description
Technical field
The present invention relates to polyether sulfone preparation field, polyether sulfone and its preparation side of a kind of specific side chain containing more Sulfonic acid structures
Method.
Background technique
In the past few decades, since poly (ether sulfone) film has excellent mechanical strength, filming performance, heat resistance and resistance to
Chemical property, to obtain universal approval and extensive commercial application, and polyether sulfone conduct in many fields such as Water warfare
Contacting blood material has relatively good biocompatibility compared to other materials.However, the hydrophobicity of polyether sulfone also answers it
Used time, there are some disadvantages, and as that can cause because of its hydrophobicity when being used as material for water treatment, membrane resistance is big, flux is small and easily dirty
Dye can lead to protein absorption, platelet adhesion reaction and blood clotting etc. no because of its hydrophobicity when as contacting blood material
Good reaction.Therefore, there is an urgent need to be modified to polyether sulfone to improve its hydrophily and blood compatibility.
It is well known that heparin is considered a kind of well for anticoagulant biology in application contacting blood material
Molecule, there are many report that Immobilized Heparin is improved to the blood compatibility of polymer material, most common method is first
Surface modification makes Immobilized Heparin again, and in addition there are the methods of whole body test tube of hepari, plasma surface treatment redeposition heparin.
105833748 A of Chinese patent CN, which is disclosed, a kind of to be added to heparin in casting solution so that polyacrylonitrile film is complete
The method of body test tube of hepari, the PS membrane that 105311974 A of Chinese patent CN discloses a kind of surface carboxylation are grafted heparin again
Method, 102258946 A of Chinese patent CN disclose a kind of method of the PS membrane deposition heparin of corona treatment；Whole body
The film of test tube of hepari easily leads to serious hemorrhage complication when being used as haemodialysis, and the covalent bond between heparin and polymer may
It is poly- for heparin to be grafted to due to being broken in heparinnized materials use process there are different chemistry or biotic environment
The method closed on object material generally requires longer reaction time and stringent program.Above-mentioned heparin fixing means exists
Inconvenience, which has limited the applications of heparin modified material.
Therefore, many passes are received come the method on decorative material surface by introducing functional group such as sulfonic acid and carboxylic acid group
Note, because they can partially imitate heparin, shows the similar bioactivity in or part similar to heparin, these imitate heparin
The polymer of structure is referred to as imitative heparin polymer.
The present invention utilizes relatively easy preparation method, by introducing more Sulfonic acid structures in polymer molecule side-chain structure
And polyethylene glycol structures, the hydrophily and biocompatibility of polymer are effectively improved, imitation heparin structure and function have been reached
Purpose.
Summary of the invention
The purpose of the present invention is to provide a kind of hydrophily that can effectively improve after polymer film forming and biocompatibilities
The side chain of imitative heparin function is containing the polyether sulfone of more Sulfonic acid structures.
A kind of polyether sulfone of the side chain containing more Sulfonic acid structures, structural formula are
M indicates the quantity of polyethylene glycol repetitive unit in formula, is the integer of 22-228；N indicates polyether sulfone repetitive unit
Quantity is the integer of 429-860；L indicates the quantity of sulfonated chemical structure unit, is the integer of 15-150.
The polyethylene glycol block that the side chain that the present invention obtains has on the polyether sulfone containing more Sulfonic acid structures, the polymerization made
The hydrophily of object film has obtained apparent improvement；Meanwhile the multiple sulfonic groups having on polymer lateral chain play simulation heparin
Function, preferably improve the blood compatibility and cell compatibility being film-made by polymer.
A kind of preparation method of polyether sulfone the present invention also provides side chain containing more Sulfonic acid structures, includes the following steps:
(1) polyether sulfone powder is completely dissolved in the concentrated sulfuric acid, chloromethyl ether is added dropwise under the conditions of 4-6 DEG C, reacted 3-5 hours, it will
Chloromethylation polyether sulfone is obtained after acquired solution processing；
(2) under nitrogen protection, chloromethylation polyether sulfone and sodium carbonate that step (1) obtains are completely dissolved in N, N- diformazan
In yl acetamide, the polyglycol solution for being dissolved in n,N-dimethylacetamide is added dropwise under the conditions of 65-75 DEG C, reacts 3-5 hours,
Pegylation polyether sulfone is obtained after acquired solution is handled；
(3) under condition of ice bath, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is dissolved in chloroform
Solution A is obtained, then Pegylation polyether sulfone, 4- cyano -4- (dodecyl sulfanyl thiocarbonyl) that step (2) is obtained
Sulfanyl valeric acid and 4-dimethylaminopyridine are dissolved in chloroform and obtain solution B, and solution A is added drop-wise in solution B, is added dropwise
After be warming up to 30-40 DEG C of reaction 22-25 hours, the Pegylation that three thioester group of band is obtained after acquired solution is handled gathers
Ether sulfone；
(4) under nitrogen protection, the Pegylation polyether sulfone and 2- third of three thioester group of band step (3) obtained
Acrylamide -2- methyl propane sulfonic acid is completely dissolved in n,N-dimethylacetamide, and azodiisobutyronitrile is added, is warming up to 65-75 DEG C
Polymerization reaction 22-25 hours, polyether sulfone of the side chain containing more Sulfonic acid structures is obtained after acquired solution is handled.
The specific synthetic route of polyether sulfone of the side chain that the present invention obtains containing more Sulfonic acid structures is as follows:
In the step (1), the mass ratio of polyether sulfone, the concentrated sulfuric acid and chloromethyl ether is 1:18-19:1.6-1.7.
In the step (2), chloromethylation polyether sulfone, sodium carbonate, polyethylene glycol, n,N-dimethylacetamide mass ratio
For 1:1:2-20:7-60.
In the step (3), 4- cyano -4- (dodecyl sulfanyl thiocarbonyl) sulfanyl valeric acid, 1- (3- diformazan ammonia
Base propyl) -3- ethyl-carbodiimide hydrochloride, 4-dimethylaminopyridine, Pegylation polyether sulfone, chloroform mass ratio
For 1:1.2:0.3-0.4:4-25:20-50.
In the step (4), Pegylation polyether sulfone, azodiisobutyronitrile, 2- acrylamide-2-methyl propane sulfonic and
The mass ratio of DMAC N,N' dimethyl acetamide is 1:0.0015-0.01:2-3:7.5-8.5.
Preferably, in step (1), the partial size of polyether sulfone powder is 1~2 μm.
Preferably, in step (1), the weight average molecular weight of polyether sulfone powder is 20000~250000, further preferably
100000~200000, obtained polymer film forming better performances.
Preferably, in step (2), the molecular weight of polyethylene glycol is 1000-10000.
Compared with the prior art, the present invention has the following beneficial effects:
(1) the PEG section having on the polyether sulfone obtained by the present invention makes the hydrophily of film obtain apparent improvement, and
The multiple sulfonic groups having then play the function of simulation heparin, preferably improve the blood compatibility being film-made by polymer
And cell compatibility；
(2) covalent bond between the multiple sulfonic acid groups and polyether sulfone strand on the polymer lateral chain obtained by the present invention
Effect keeps multi-sulfonic group stability carried on poly (ether sulfone) film obtained good, not easily runs off；
(3) the method for the present invention preparation process is simple, cost is more cheap.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure for polyether sulfone of the side chain containing more Sulfonic acid structures that embodiment 1 obtains.
Specific embodiment
Embodiment 1
(1) the 180g concentrated sulfuric acid (98%), the polyether sulfone powder that 10g partial size is 1.5 μm are added to three mouthfuls of circles of belt stirrer
In the flask of bottom, agitator speed is adjusted to 800r/min and sub-cooled circulating pump is moved into, in 5 DEG C of temperature after solid is completely dissolved
Acquired solution is poured into the deionized water being stirred after reaction 4 hours, white is collected by filtration by the lower chloromethyl ether that 16g is added dropwise of degree
Solid, then white solid is washed repeatedly until neutrality, finally dries the vacuum that gained white solid is placed in 80 DEG C with deionized water
It is 24 hours dry in case, obtain chloromethylation polyether sulfone；
(2) under nitrogen protection, chloromethylation polyether sulfone, 5g sodium carbonate and the 20g N, N- bis- 5g step (1) obtained
Methylacetamide, which is placed in the three neck round bottom flask of belt stirrer, obtains solution A, then 10g cetomacrogol 1000 is dissolved in 15g's
Solution B is obtained in n,N-dimethylacetamide, and solution B is added dropwise in solution A under the conditions of 70 DEG C and is reacted 4 hours, it will
Reaction acquired solution is added in the dehydrated alcohol that is stirred continuously, and white solid is collected by filtration, then after being washed repeatedly with deionized water
Drying 24 hours in 70 DEG C of vacuum drying oven are placed in, Pegylation polyether sulfone is obtained；
(3) under condition of ice bath, 12g 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is dissolved in 50g
Chloroform after obtain solution A, then Pegylation polyether sulfone, 10g 4- cyano -4- (12 that 40g step (2) is obtained
Alkyl alkylthio base thiocarbonyl) sulfanyl valeric acid and 3g 4-dimethylaminopyridine be dissolved in 150g chloroform and obtain solution B,
Solution A is instilled in the solution B being stirred continuously, 35 DEG C are warming up to after being added dropwise and is reacted 24 hours, reaction acquired solution is added
Enter in the ether being stirred continuously, faint yellow solid is collected by filtration, then is washed repeatedly with ether and be placed on the vacuum that temperature is 40 DEG C
It is 24 hours dry in baking oven, obtain the Pegylation polyether sulfone of three thioester group of band；
(4) the Pegylation polyether sulfone for three thioester group of band for obtaining 200g step (3), 400g 2- acryloyl
Amine -2- methyl propane sulfonic acid and 1500g DMAC N,N' dimethyl acetamide are added to be burnt with three mouthfuls of round bottoms of agitating device and logical nitrogen device
In bottle, after completely dissolution to solid, 2g azodiisobutyronitrile is added, control nitrogen flow rate is 40mL/min, is passed through nitrogen 30 and divides
Zhong Hou, is warming up to 70 DEG C of RAFT polymerization reactions 24 hours, will react acquired solution and is added in the ether being stirred continuously, is collected by filtration
Faint yellow solid, then washed repeatedly with ether and be placed on drying 24 hours in the vacuum drying oven that temperature is 40 DEG C, obtain the side
Polyether sulfone of the chain containing more Sulfonic acid structures, characterizing its molecular weight through gel permeation chromatography is about 1523000.
Polyether sulfone to obtained side chain containing more Sulfonic acid structures carries out nuclear-magnetism characterization, as a result as shown in Figure 1, as seen from the figure: δ
Peak at=8.05-8.27 corresponds on the nitrogen-atoms on hydrogen and AMPS block on the phenyl ring of the benzyl group in polyethers sulfone main chain
Hydrogen；Peak at δ=7.84-8.07 corresponds to the hydrogen in polyethers sulfone main chain on the phenyl ring at sulfuryl ortho position；At δ=7.16-7.38
Peak corresponds to the hydrogen in polyethers sulfone main chain on the phenyl ring of sulfuryl meta position；Peak at δ=4.71-4.86 corresponds on polyethers sulfone main chain benzyl
Methylene hydrogen；Peak at δ=3.51-3.72 corresponds to the hydrogen of methylene on polyethylene glycol block；At δ=2.81-2.99
Hydrogen on the hydrogen on methylene being connected on peak corresponding A MPS block with sulfonic group and the methylene being connected with three thio ester groups；
The secondary first of the hydrogen and AMPS block on the corresponding methylene being connected with the ester group of polyether sulfone side chain in peak at δ=2.01-2.25
The hydrogen of base；Peak at δ=1.75-1.99 corresponds to the main chain of the hydrogen of the methylene of the position β of the ester group of polyether sulfone side chain, AMPS block
On methylene hydrogen and three thio ester groups the position β methylene hydrogen；Peak at δ=1.29-1.49 corresponds to polyether sulfone side
The hydrogen of methyl on the quaternary carbon of chain, methyl on AMPS block hydrogen and be connected with the methylene of the position β of three thio ester groups
The hydrogen of methylene on ten straight chained alkyl of carbon.Therefore, polymers obtained structure can be confirmed by nuclear magnetic spectrogram.
Embodiment 2
(1) the 190g concentrated sulfuric acid (98%), the polyether sulfone powder that 10g partial size is 1.5 μm are added to three mouthfuls of circles of belt stirrer
In the flask of bottom, agitator speed is adjusted to 800r/min and sub-cooled circulating pump is moved into, in 5 DEG C of temperature after solid is completely dissolved
Acquired solution is poured into the deionized water being stirred after reaction 4 hours, white is collected by filtration by the lower chloromethyl ether that 17g is added dropwise of degree
Solid, then white solid is washed repeatedly until neutrality, finally dries the vacuum that gained white solid is placed in 80 DEG C with deionized water
It is 24 hours dry in case, obtain chloromethylation polyether sulfone；
(2) under nitrogen protection, chloromethylation polyether sulfone, 5g sodium carbonate and the 50g N, N- bis- 5g step (1) obtained
Methylacetamide, which is placed in the three neck round bottom flask of belt stirrer, obtains solution A, then 100g polyethylene glycol 10000 is dissolved in 250g
N,N-dimethylacetamide in obtain solution B, solution B is added dropwise in solution A under the conditions of 70 DEG C and is reacted 4 hours,
Acquired solution will be reacted to be added in the dehydrated alcohol being stirred continuously, white solid is collected by filtration, then washed repeatedly with deionized water
Drying 24 hours in 70 DEG C of vacuum drying oven are placed on, Pegylation polyether sulfone is obtained；
(3) under condition of ice bath, 12g 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is dissolved in 100g
Chloroform after obtain solution A, then Pegylation polyether sulfone, 10g 4- cyano -4- (ten that 250g step (2) is obtained
Dialkyl group sulfanyl thiocarbonyl) sulfanyl valeric acid and 4g4- dimethylamino naphthyridine be dissolved in 150g chloroform and obtain solution B,
Solution A is instilled in the solution B being stirred continuously, 40 DEG C are warming up to after being added dropwise and is reacted 24 hours, reaction acquired solution is added
Enter in the ether being stirred continuously, faint yellow solid is collected by filtration, then is washed repeatedly with ether and be placed on the vacuum that temperature is 40 DEG C
It is 24 hours dry in baking oven, obtain the Pegylation polyether sulfone of three thioester group of band；
(4) the Pegylation polyether sulfone for three thioester group of band for obtaining 200g step (3), 600g 2- acryloyl
Amine -2- methyl propane sulfonic acid and 1700g DMAC N,N' dimethyl acetamide are added to be burnt with three mouthfuls of round bottoms of agitating device and logical nitrogen device
In bottle, after completely dissolution to solid, 0.3g azodiisobutyronitrile is added, control nitrogen flow rate is 40mL/min, is passed through nitrogen 30
After minute, it is warming up to 70 DEG C of RAFT polymerization reactions 24 hours, acquired solution will be reacted and be added in the ether being stirred continuously, filtering is received
Collect faint yellow solid, then washed repeatedly with ether and be placed on drying 24 hours in the vacuum drying oven that temperature is 40 DEG C, obtains described
Polyether sulfone of the side chain containing more Sulfonic acid structures, characterizing its molecular weight through gel permeation chromatography is about 1954000.
Embodiment 3
(1) the 185g concentrated sulfuric acid (98%), the polyether sulfone powder that 10g partial size is 1.5 μm are added to three mouthfuls of circles of belt stirrer
In the flask of bottom, agitator speed is adjusted to 800r/min and sub-cooled circulating pump is moved into, in 5 DEG C of temperature after solid is completely dissolved
Acquired solution is poured into the deionized water being stirred, is collected by filtration white after reaction 4 hours by the lower chloromethyl ether that 16.5g is added dropwise of degree
Color solid, then white solid is washed repeatedly until gained white solid, is finally placed in 80 DEG C of vacuum by neutrality with deionized water
It is 24 hours dry in baking oven, obtain chloromethylation polyether sulfone；
(2) under nitrogen protection, chloromethylation polyether sulfone, 5g sodium carbonate and the 30g N, N- bis- 5g step (1) obtained
Methylacetamide, which is placed in the three neck round bottom flask of belt stirrer, obtains solution A, then 50g polyethylene glycol 5000 is dissolved in 200g's
Solution B is obtained in n,N-dimethylacetamide, and solution B is added dropwise in solution A under the conditions of 70 DEG C and is reacted 4 hours, it will
Reaction acquired solution is added in the dehydrated alcohol that is stirred continuously, and white solid is collected by filtration, then after being washed repeatedly with deionized water
Drying 24 hours in 70 DEG C of vacuum drying oven are placed in, Pegylation polyether sulfone is obtained；
(3) under condition of ice bath, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt that 12g step (2) is obtained
Hydrochlorate obtains solution A after being dissolved in the chloroform of 50g, then Pegylation polyether sulfone, 10g 4- that 150g step (2) is obtained
Cyano -4- (dodecyl sulfanyl thiocarbonyl) sulfanyl valeric acid and 4g 4-dimethylaminopyridine are dissolved in 300g chloroform
In obtain solution B, solution A is instilled in the solution B that is stirred continuously, 36 DEG C are warming up to after being added dropwise and is reacted 24 hours, will be anti-
It answers acquired solution to be added in the ether being stirred continuously, faint yellow solid is collected by filtration, then washed repeatedly with ether and be placed on temperature
It is drying 24 hours in 40 DEG C of vacuum drying ovens, obtains the Pegylation polyether sulfone of three thioester group of band；
(4) the Pegylation polyether sulfone for three thioester group of band for obtaining 200g step (3), 500g 2- acryloyl
Amine -2- methyl propane sulfonic acid and 1600g DMAC N,N' dimethyl acetamide are added to be burnt with three mouthfuls of round bottoms of agitating device and logical nitrogen device
In bottle, after completely dissolution to solid, 1.2g azodiisobutyronitrile is added, control nitrogen flow rate is 40mL/min, is passed through nitrogen 30
After minute, it is warming up to 70 DEG C of RAFT polymerization reactions 24 hours, acquired solution will be reacted and be added in the ether being stirred continuously, filtering is received
Collect faint yellow solid, then washed repeatedly with ether and be placed on drying 24 hours in the vacuum drying oven that temperature is 40 DEG C, obtains described
Polyether sulfone of the side chain containing more Sulfonic acid structures, characterizing its molecular weight through gel permeation chromatography is about 1745000.
Embodiment 4
(1) the 187g concentrated sulfuric acid (98%), the polyether sulfone powder that 10g partial size is 1.5 μm are added to three mouthfuls of circles of belt stirrer
In the flask of bottom, agitator speed is adjusted to 800r/min and sub-cooled circulating pump is moved into, in 5 DEG C of temperature after solid is completely dissolved
Acquired solution is poured into the deionized water being stirred, is collected by filtration white after reaction 4 hours by the lower chloromethyl ether that 16.7g is added dropwise of degree
Color solid, then white solid is washed repeatedly until gained white solid, is finally placed in 80 DEG C of vacuum by neutrality with deionized water
It is 24 hours dry in baking oven, obtain chloromethylation polyether sulfone；
(2) under nitrogen protection, chloromethylation polyether sulfone, 5g sodium carbonate and the 30g N, N- bis- 8g step (1) obtained
Methylacetamide, which is placed in the three neck round bottom flask of belt stirrer, obtains solution A, then 70g polyethylene glycol 7000 is dissolved in 230g's
Solution B is obtained in n,N-dimethylacetamide, and solution B is added dropwise in solution A under the conditions of 70 DEG C and is reacted 4 hours, it will
Reaction acquired solution is added in the dehydrated alcohol that is stirred continuously, and white solid is collected by filtration, then after being washed repeatedly with deionized water
Drying 24 hours in 70 DEG C of vacuum drying oven are placed in, Pegylation polyether sulfone is obtained；
(3) under condition of ice bath, 12g 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is dissolved in 50g
Chloroform after obtain solution A, then Pegylation polyether sulfone, 10g 4- cyano -4- (ten that 200g step (2) is obtained
Dialkyl group sulfanyl thiocarbonyl) sulfanyl valeric acid and 4g 4-dimethylaminopyridine be dissolved in 400g chloroform and obtain solution
B instills solution A in the solution B being stirred continuously, and 40 DEG C are warming up to after being added dropwise and is reacted 24 hours, acquired solution will be reacted
It is added in the ether that is stirred continuously, faint yellow solid is collected by filtration, then wash with ether that be placed on temperature true for 40 DEG C repeatedly
It is 24 hours dry in empty baking oven, obtain the Pegylation polyether sulfone of three thioester group of band；
(4) the Pegylation polyether sulfone for three thioester group of band for obtaining 200g step (3), 550g 2- acryloyl
Amine -2- methyl propane sulfonic acid and 1700g DMAC N,N' dimethyl acetamide are added to be burnt with three mouthfuls of round bottoms of agitating device and logical nitrogen device
In bottle, after completely dissolution to solid, 1.7g azodiisobutyronitrile is added, control nitrogen flow rate is 40mL/min, is passed through nitrogen 30
After minute, it is warming up to 70 DEG C of RAFT polymerization reactions 24 hours, acquired solution will be reacted and be added in the ether being stirred continuously, filtering is received
Collect faint yellow solid, then washed repeatedly with ether and be placed on drying 24 hours in the vacuum drying oven that temperature is 40 DEG C, obtains described
Polyether sulfone of the side chain containing more Sulfonic acid structures, characterizing its molecular weight through gel permeation chromatography is about 1826000.
Polyether sulfone and unmodified polyether sulfone by the obtained side chain of embodiment 1-4 containing more Sulfonic acid structures be respectively coated in
On glass plate, polymer film is obtained after film forming, and polymer film is tested.
The water contact angle of sessile drop method test polymer film is first used, then anticoagulation experiment is carried out to polymer film: will
0.1mL37 DEG C is gone the anticoagulant blood plasma addition of calcium human body to be coated in the teat glass of polymer film, adds 0.1mL's
0.025mol/L calcium chloride solution immerses 37 DEG C of waters bath with thermostatic control, manual time-keeping, and record manages the interior time for white filiform occur,
It repeats to survey 5 times, be averaged.
Test polymer film the data obtained is as shown in the table:
| Water contact angle (°) | The multiple calcification time (s) | |
| It is unmodified | 70 | 160 |
| Embodiment 1 | 60 | 200 |
| Embodiment 2 | 58 | 190 |
| Embodiment 3 | 59 | 193 |
| Embodiment 4 | 59 | 188 |
Test result shows: after polyether sulfone film forming of the side chain that the present invention obtains containing more Sulfonic acid structures, the water contact angle of film
It reduces, hydrophily has obtained apparent improvement；Meanwhile when multiple calcification of the embodiment resulting polymers film in anticoagulation experiment
Between extended compared with unmodified membrane, therefore its biocompatibility has also obtained apparent improvement.
Claims (9)
1. a kind of polyether sulfone of side chain containing more Sulfonic acid structures, which is characterized in that its molecular structural formula are as follows:
In formula, m 22-228, n 429-860, l are the integer of 15-150.
2. a kind of preparation method of polyether sulfone of the side chain as described in claim 1 containing more Sulfonic acid structures, includes the following steps:
(1) polyether sulfone powder is completely dissolved in the concentrated sulfuric acid, chloromethyl ether is added dropwise under the conditions of 4-6 DEG C, reacted 3-5 hours, by gained
Chloromethylation polyether sulfone is obtained after solution processing；
(2) under nitrogen protection, chloromethylation polyether sulfone and sodium carbonate that step (1) obtains are completely dissolved in N, N- dimethyl second
In amide, the polyglycol solution for being dissolved in n,N-dimethylacetamide is added dropwise under the conditions of 65-75 DEG C, reacts 3-5 hours, by institute
Pegylation polyether sulfone is obtained after obtaining solution processing；
(3) under condition of ice bath, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is dissolved in chloroform and is obtained
Solution A, then Pegylation polyether sulfone, 4- cyano -4- (dodecyl sulfanyl thiocarbonyl) sulfane that step (2) is obtained
Base valeric acid and 4-dimethylaminopyridine are dissolved in chloroform and obtain solution B, and solution A is added drop-wise in solution B, rise after being added dropwise
Temperature to 30-40 DEG C reaction 22-25 hours, the Pegylation polyethers of three thioester group of band is obtained after acquired solution is handled
Sulfone；
(4) under nitrogen protection, the Pegylation polyether sulfone and 2- acryloyl of three thioester group of band step (3) obtained
Amine -2- methyl propane sulfonic acid is completely dissolved in n,N-dimethylacetamide, and azodiisobutyronitrile is added, is warming up to 65-75 DEG C of polymerization
Reaction 22-25 hours, obtains polyether sulfone of the side chain containing more Sulfonic acid structures after acquired solution is handled.
3. the preparation method of polyether sulfone of the side chain according to claim 2 containing more Sulfonic acid structures, which is characterized in that step
(1) in, the mass ratio of the polyether sulfone, the concentrated sulfuric acid and chloromethyl ether is 1:18-19:1.6-1.7.
4. the preparation method of polyether sulfone of the side chain according to claim 2 containing more Sulfonic acid structures, which is characterized in that step
(2) in, the chloromethylation polyether sulfone, sodium carbonate, polyethylene glycol, n,N-dimethylacetamide mass ratio be 1:1:2-
20:7-60。
5. the preparation method of polyether sulfone of the side chain according to claim 2 containing more Sulfonic acid structures, which is characterized in that step
(3) in, the 4- cyano -4- (dodecyl sulfanyl thiocarbonyl) sulfanyl valeric acid, 1- (3- dimethylamino-propyl) -3-
Ethyl-carbodiimide hydrochloride, 4-dimethylaminopyridine, Pegylation polyether sulfone and chloroform mass ratio be 1:1.2:
0.3-0.4:4-25:20-50。
6. the preparation method of polyether sulfone of the side chain according to claim 2 containing more Sulfonic acid structures, which is characterized in that step
(4) in, the Pegylation polyether sulfone, azodiisobutyronitrile, 2- acrylamide-2-methyl propane sulfonic and N, N- dimethyl
The mass ratio of acetamide is 1:0.0015-0.01:2-3:7.5-8.5.
7. the preparation method of polyether sulfone of the side chain according to claim 2 containing more Sulfonic acid structures, which is characterized in that step
(1) in, the partial size of the polyether sulfone powder is 1-2 μm.
8. the preparation method of polyether sulfone of the side chain according to claim 2 containing more Sulfonic acid structures, which is characterized in that step
(1) in, the weight average molecular weight of the polyether sulfone powder is 20000-250000.
9. the preparation method of polyether sulfone of the side chain according to claim 2 containing more Sulfonic acid structures, which is characterized in that step
(2) in, the molecular weight of the polyethylene glycol is 1000-10000.
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)
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