CN1844175A - Method for graft modification of polyethersulfone - Google Patents
Method for graft modification of polyethersulfone Download PDFInfo
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- CN1844175A CN1844175A CN 200510025006 CN200510025006A CN1844175A CN 1844175 A CN1844175 A CN 1844175A CN 200510025006 CN200510025006 CN 200510025006 CN 200510025006 A CN200510025006 A CN 200510025006A CN 1844175 A CN1844175 A CN 1844175A
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Abstract
This invention is the method of polyethersulfone grafting to modify properties. Its characteristic is exposing polyethersulfone powder and andacroleic acid monomer directly to gamma-ray for grafting. The polyethersulfone obtain in this invention has hydrophilicity. The following product polyethersulfone film has hydrophilicity to reduce the jamming possibility in film grafting. So the better permeability and filteration is gained.
Description
Technical field
The present invention relates to a kind of method of graft modification of polyethersulfone.
Background technology
The annual sales amount of membrane separation technique product is about 5,000,000,000 dollars in the world at present, and annual growth is 8%-15%.By inference, by 2005, the market sales revenue of world's separatory membrane will reach hundred million dollars of 80-100.By 2010, the gross sales (GS) in film market, the world will reach hundred million dollars of 110-135.The annual sales amount of internal membrane technical products is about hundred million yuans of 10-15, and annual growth is about 15%, and considerably beyond the rate of growth of world GDP and domestic GDP, its development potentiality and space are very huge respectively.
Current, the major obstacle of restriction membrane technique industrialization is that film pollutes.Selecting the suitable membrane material or carry out the modification of mould material, is the effective way that prevents that film from polluting.Generally speaking, the work-ing life that the film of process modification can improve film greatly, improve the continuous work-ing life of film relatively, reduced the use cost of film, can satisfy film harsh requirement aspect the serialization processing in enormous quantities in desalt, sewage disposal, hemodialysis, foodstuffs industry.
Polyethersulfone (Polyethersulfone is abbreviated as PES) is the engineering plastics of developed recently a kind of excellent property of getting up.Molecular structural formula is:
Polyethersulfone has obtained application widely in the following areas owing to have advantages such as intensity height, high temperature resistant (use temperature can reach 120 ℃), corrosion-resistant, anti-oxidant, pH value wide accommodation:
1) coil rack on electrical equipment, the electronic industry, track circuit card, time switch etc.;
2) make retainer, gear, precision instrument part etc. on the mechanical industry;
3) use material and structured material on the aircraft industry in the cabin;
4) the various component of anti-gasoline, machine oil on the automotive industry;
5) in-line pump of using of industrial various medical machineries of dietetic food and foodstuff production equipment etc.;
6) impregnating material, ultra-filtration membrane etc.
The appearance of poly (ether sulfone) film has greatly advanced the development of membrane filtration technology, yet it is the same with all modern films, poly (ether sulfone) film is polluted in actual use easily, thereby causes flux a series of problems such as significantly reduction, shortening in work-ing life, production cost increase rapidly.It is the obstruction that ultrafiltration membrane technique is further applied that film pollutes, and is the current key issue that needs to be resolved hurrily in the application from now on that reaches.
According to the viewpoint of solution thermodynamics, Nonpolar Solute is easily adsorbed at nonpolar interface in polar solvent.Owing to lack for example hydrophilic radical of hydroxyl, carboxyl, amino, sulfydryl one class in the polyethersulfone chemical structure, show stronger hydrophobicity, cause be that the film surface that raw material preparing obtains also presents stronger hydrophobicity.Therefore, poly (ether sulfone) film pollutes with its hydrophobicity closely related.Obviously, polyethersulfone is carried out modification, promptly in the polyethersulfone chemical structure, introduce hydrophilic radical, be expected to solve effectively the poly (ether sulfone) film pollution problem.
At present polyethersulfone being carried out modification all is to be institute's film forming to be carried out surface treatment to improve film surface hydrophilic performance after the base material film forming with the polyethersulfone basically.Common means comprise uses tensio-active agent, chemical modification, plasma modification, photochemical modification, radiation modification etc.Chemical process generally is to adopt sulfonated method sulfonic acid group on film surface grafting to improve film to proteinic contamination resistance to change the hydrophilicity on film surface.But because the chemical stability of the excellence of polyethersulfone body make and must use strong acid and strong base as reaction reagent in chemical modification, but strong acid and strong base can cause the polyethersulfone degraded, thereby greatly reduce the mechanical property of polyethersulfone itself; UV-light initiation grafting polymeric effective wavelength is about 254nm, but polyethersulfone body radiation degradation is comparatively obvious under this wavelength; The graft polymerization that plasma body causes usually occurs in the end that the polyethersulfone molecular chain is positioned at outermost surface usually, when after use after a while, because sub-chain motion can be covered by other segment through the end of modification, thereby reduce its antifouling property.
Compare with aforesaid method, utilize radiotechnology, particularly gamma-ray irradiation carries out graft modification to polyethersulfone and has significant advantage: (1) is owing to exist aromatic group in the chemical structure, polyethersulfone has certain radiation resistance, therefore utilize radiation polarity technology on the polyethersulfone molecular chain, to introduce polar functional group, can on the basis that keeps the original mechanical property of polyethersulfone, give polyethersulfone new performance; (2) radiation-induced graft copolymerization can directly be caused by ray, does not need initiator, therefore can obtain purified graft copolymer; (3) radiation grafting polymerization can be carried out under room temperature even low temperature; (4) radiation-induced graft copolymerization can carry out under solid-state, liquid, solid-liquid state, can alleviate the problem that needs that the chemical graft reaction often runs into use a large amount of solvents; (5) radiation-induced graft copolymerization has homogeneity and controllability preferably.Above advantage makes the polyethersulfone radiation grafting realize that industrialization becomes possibility.
At present, the main gamma-ray irradiation that uses carries out graft modification to the polyethersulfone finished film, but find: when increasing percentage of grafting, then exist the working efficiency that causes film because grafted monomer segment stops up fenestra to descend, influenced the defective of the practical effect of film for improving the film wetting ability.And film forming can be avoided this problem effectively after the material before the polyethersulfone film forming directly carried out modification, but at present this product or report are not arranged as yet.
Summary of the invention
The inventor has carried out above-mentioned trial, and purpose is for addressing the above problem, and a kind of method of graft modification of polyethersulfone different from the past is provided.
The objective of the invention is to realize by following technical proposal: a kind of method of graft modification of polyethersulfone is characterized in that polyethersulfone powder and acrylic monomer are carried out the gamma-ray irradiation graft reaction.
Wherein, the weight ratio of this polyethersulfone powder and acrylic monomer preferably is 1: 0.1-5 more preferably is 1: 0.16-4.21; The volumetric concentration of this acrylic monomer is 2-50%, preferably is 10-45%.
The monomer of this graft modification can be the various monomers of existing poly (ether sulfone) film graft modification, as the acrylic monomer of hydrophilic radicals such as hydroxyl such as vinylformic acid, methacrylic acid, hydroxy acrylate or amino, or polyoxyethylene glycol etc.
The same with existing poly (ether sulfone) film graft reaction, for suppressing the homopolymerization between the acrylic monomer, be preferably in this reaction system and be added with stopper.This stopper can be Cu
2+Or Fe
2+Salt (Mohamed Mahmoud Nasef.Preparation and applications of ion exchangemembranes by radiation-induced graft copolymerization of polar monomers ontonon-polar films.Prog.Polym.Sci.29 (2004) 499-561), in the present invention, its concentration in reaction system is preferably 0.001-0.04mol/L.
Reaction of the present invention is preferably carried out under pH is the condition of 0.5-6.0.
It is 1.88-30kGy that the present invention preferably adopts total dose, and the mean dose rate is 0.100-0.347, and gamma-ray irradiation is carried out in the cobalt source of preferred 0.1-0.324kGy/h.
Be film forming better later on, the inventive method also comprised further treatment step removing impurity such as homopolymer, as the product extracting that aforesaid method made with three distilled water at least 72 hours; And it is dry to remove moisture as far as possible, preferred vacuum-drying.
What the present invention adopted is commercialization polyethersulfone powder, and its median size is 0.01mm.Certainly well-known, the particle diameter of reactant is more little, and its reaction table area is bigger, promptly more helps reaction, therefore, and the preferred polyethersulfone powder of the present invention median size≤0.01mm.
The present invention adopts powder directly as material modified, has the following advantages:
1) specific surface area is big, and flow of matter characteristic such as solid solvability also improves thereupon, some bounded participation processes can fully be carried out, for chemical reaction provides enough big surface-area;
2) after macromolecular material makes its efflorescence by means of external force, reduce the adjacent coexisting state of crystalline region and non-crystalline region in the primary structure, made the noncrystalline domain contact surface increase, helped improving reactive behavior;
3) most of particle of polymer powder body material does not always exist with solid nucleome, exists slit and hole in the particle, therefore liquid is had adsorption.
Thereby the polyethersulfone powder that adopts method of the present invention to obtain has wetting ability preferably, have clear improvement with grafted polyethersulfone powder comparison wetting ability not, to no longer need graft modification after the film forming, thereby avoid causing the working efficiency of film to descend because of film grafted monomer segment stops up fenestra, influenced the practical effect of film, thereby improved the work-ing life of film.
Description of drawings
The infared spectrum of the product that Fig. 1 makes for the inventive method.
Embodiment
Further specify the effect of operating process of the present invention and product below with embodiment, but the present invention is not limited to this.
Wherein, the present invention is that example is tested with the acrylic monomer, and it is example that the following example has further been selected Acrylic Acid Monomer wherein for use, and this polyethersulfone powder is that commercially available (median size is 0.01mm for Indian, Garda) product.Adopt infrared spectrometer (Nicolet, Avater360 type) to detect graft effect; Powder after the modification with infrared tabletting machine compressing tablet, is used contact angle instrument (dataphysis, OCA20) contact angle of measurement water PES powder surface after modification then; Quality before and after the grafting of weighing polyethersulfone powder is calculated as follows percentage of grafting.
Percentage of grafting=(W-W
o)/W
o* 100%
W wherein
o, W is respectively the quality before and after the sample grafting.
In addition,, above-mentioned commercialization polyethersulfone powder is carried out pre-treatment for testing back infrared measurement needs, as with three distilled water extractings total more than 24 hours with the contained additive of removal polyethersulfone.
Embodiment 1～7
The pretreated polyethersulfone powder of 5g is put into irradiation tube, add the acrylic acid aqueous solution (PES: Acrylic Acid Monomer is 5: 21.04) of 40ml, 50% (v/v), add CuSO again
4As stopper, and to make its concentration in reaction system be 0.004mol/L, with the HCl aqueous solution regulation system pH value to 1.0 of 1mol/L.Then irradiation tube is placed on irradiation under the cobalt source, radiation modification (as shown in table 1) is carried out in the experiment that different cobalt-60 radiosterilize total doses is set, and the mean dose rate is 0.324kGy/h.Sample is taken out, use more than three distilled water extracting 72h again, vacuum-drying is to constant weight in 100 degrees centigrade vacuum drying oven.
Measure the contact angle of water PES powder surface after modification with contact angle instrument; And the percentage of grafting of calculating PEI powder, detected result is as shown in table 1.
The embodiment of the different total radiation doses of table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Irradiation dose (kGy) | 1.88 | 7.24 | 9.36 | 14.72 | 16.81 | 22.17 | 24.23 |
| Percentage of grafting (%) | 33.5 | 36.4 | 38.3 | 41.3 | 47.7 | 49.1 | 67.8 |
| Contact angle | 64.5 | 59.8 | 56.4 | 50.1 | 45.1 | 42.1 | 32.0 |
| The blank sample contact angle | 72.6 | ||||||
Embodiment 8～10
The cobalt-60 radiosterilize total dose is made as 5kGy, different mean dose rates is set carries out radiation modification (as shown in table 2).Surplus with embodiment 1, detected result is as shown in table 2.
The embodiment of the different mean dose rates of table 2
| Embodiment | 8 | 9 | 10 |
| Mean dose rate (kGy/h) | 0.100 | 0.220 | 0.324 |
| Percentage of grafting (%) | 7.4 | 10.8 | 37.8 |
| Contact angle | 71.2 | 68.2 | 63.1 |
| The blank sample contact angle | 72.6 | ||
Embodiment 11～15
The pretreated polyethersulfone powder of 5g is put into irradiation tube, the acrylic acid aqueous solution 40ml (as shown in table 3) that adds different ratios (w/w) and volumetric concentration, irradiation tube is put into irradiation under the cobalt source, irradiation dose is 15kGy, mean dose rate 0.324kGy/h, surplus with embodiment 1, the results are shown in Table shown in 3.
The monomeric embodiment of table 3 different ratios and concentration
| Embodiment | 11 | 12 | 13 | 14 | 15 |
| Monomer concentration (v/v) PES: monomer (w/w) | 2％ 5∶0.8416 | 13％ 5∶5.4704 | 26％ 5∶10.941 | 39.4％ 5∶16.580 | 45.6％ 5∶19.189 |
| Percentage of grafting (%) | 4 | 30 | 60.1 | 52.7 | 46.9 |
| Contact angle | 71.8 | 64.0 | 37 | 40.4 | 43.7 |
| The blank sample contact angle | 72.6 | ||||
Embodiment 16～18
The pretreated polyethersulfone powder of 5g is put into irradiation tube, the acrylic acid aqueous solution 40ml that adds 50% (v/v), add other different stoppers, making its concentration in reaction system is 0.004mol/L (as shown in table 4), is 1.0 with the HCL regulation system pH value of 1mol/L.Then irradiation tube is put into cobalt-60 radiosterilize, irradiation dose is 5kGy, mean dose rate 0.324kGy/h, and surplus with embodiment 1, detected result is as shown in table 4.
The embodiment of the different stoppers of table 4
| Embodiment | 16 | 17 | 18 |
| Stopper | CuCl 2 | FeCl 2 | FeSO 4·(NH 4) 2SO 4·6H 2O |
| Percentage of grafting (%) | 32.3 | 28.7 | 22.3 |
| Contact angle | 65.1 | 66.1 | 68.6 |
| The blank sample contact angle | 72.6 | ||
Embodiment 19～22
The pretreated polyethersulfone powder of 5g is put into irradiation tube, add acrylic acid aqueous solution 40ml of 50% (v/v), add CuSO
4, make it in reaction system, have different volumetric molar concentrations (as shown in table 5), with the HCl aqueous solution regulation system pH value to 1.0 of 1mol/L.Surplus with embodiment 10, detected result is as shown in table 5.
The embodiment of the different inhibitor concentrations of table 5
| Embodiment | 19 | 20 | 21 | 22 |
| CuSO 4(mol/L) | 0.001 | 0.016 | 0.026 | 0.038 |
| Percentage of grafting (%) | 26.4 | 24.7 | 21.7 | 19 |
| Contact angle | 69.2 | 68.0 | 63.1 | 69.4 |
| The blank sample contact angle | 72.6 | |||
Embodiment 23～26
With acid (as HCl or the H of 1mol/L
2SO
4) or the pH value (as shown in table 6) of alkali (as the NaOH of 1mol/L) regulation system, cobalt-60 radiosterilize dosage is 5kGy, the mean dose rate is 0.324kGy/h, and is surplus with embodiment 1, the results are shown in Table shown in 6.
The embodiment of table 6 differential responses system pH
| Embodiment | 23 | 24 | 25 | 26 |
| The pH value | 0.52 | 1.0 | 3.05 | 5.58 |
| Percentage of grafting (%) | 44.43 | 39 | 41.9 | 8.73 |
| Contact angle | 40.1 | 56 | 39.6 | 69.2 |
| The blank sample contact angle | 72.6 | |||
Embodiment 27
To put into irradiation tube after the polyethersulfone powder 5g pre-treatment, add acrylic acid aqueous solution 40ml of 50% (v/v), add CuSO again
4, and to make its concentration in reaction system be 0.004mol/L.Then irradiation tube is put into cobalt-60 radiosterilize, irradiation dose is 15kGy, mean dose rate 0.324kGy/h.Surplus same
Embodiment 1.
Its percentage of grafting is 41.3%, and contact angle is 49.7.
Powder after the foregoing description extracting is dried to constant weight under 100 degrees centigrade through vacuum drying oven, test its infrared spectrum (as shown in Figure 1), the polyethersulfone powder after the discovery grafting is at 1720cm
-1The C=O peak that unmodified polyethersulfone powder does not have appears in the place, illustrates that vinylformic acid successfully is grafted to the polyethersulfone powder surface.
And measure the contact angle of water PES powder surface after modification with contact angle instrument, with grafting PES powder comparison wetting ability not have clear improvement (surface contact angle is more little, and its wetting ability is good more).
Acrylic Acid Monomer in the foregoing description is Shanghai reagent company of a Chinese Medicine group product, chemical pure; The cobalt source is
60Co, Canada provides source rod.
Claims (10)
1, a kind of method of graft modification of polyethersulfone is characterized in that polyethersulfone powder and acrylic monomer are carried out the gamma-ray irradiation graft reaction.
2, method according to claim 1, the weight ratio that it is characterized in that this polyethersulfone powder and acrylic monomer is 1: 0.1-5, the volumetric concentration of this acrylic monomer is 2-50%.
3, method according to claim 2, the volumetric concentration that it is characterized in that this acrylic monomer is 10-45%.
4, method according to claim 1 is characterized in that this acrylic monomer is an Acrylic Acid Monomer.
5, method according to claim 1 is characterized in that being added with stopper in this reaction system.
6, method according to claim 5 is characterized in that this stopper is Cu
2+Or Fe
2+Salt, its concentration in reaction system is 0.001-0.04mol/L.
7, method according to claim 1, it is characterized in that this is reflected under the condition that pH is 0.5-6.0 carries out.
8, method according to claim 1 is characterized in that it adopts total dose is 1.88-30kGy, and gamma-ray irradiation is carried out in the cobalt source of mean dose rate 0.100-0.347kGy/h.
9, method according to claim 1 is characterized in that it also comprises further treatment step: the continuous extracting of product that claim 1 is made with three distilled water at least 72 hours, and dry.
10,, it is characterized in that the median size≤0.01mm of this polyethersulfone powder according to each described method of claim 1～9.
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| CN100556926C CN100556926C (en) | 2009-11-04 |
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| CN101550222B (en) * | 2009-05-11 | 2010-09-29 | 四川省原子能研究院 | A method for preparing radiation graft copolymer of polylactic acid and N-vinyl pyrrolidone |
| CN103706266A (en) * | 2013-12-12 | 2014-04-09 | 四川大学 | In-situ polymerization mico-crosslinking polyvinylpyrrolidone modified polyether sulfone hollow fiber membrane and preparation method and use thereof |
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| US6852769B2 (en) * | 2000-10-05 | 2005-02-08 | Rensselaer Polytechnic Institute | UV-assisted grafting of PES and PSF membranes |
| CN1238406C (en) * | 2003-01-27 | 2006-01-25 | 上海高分子材料研究开发中心 | Method for preparing polymer surface modified high-crosslinking ultra-thin hydrophilic coating |
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| CN101550222B (en) * | 2009-05-11 | 2010-09-29 | 四川省原子能研究院 | A method for preparing radiation graft copolymer of polylactic acid and N-vinyl pyrrolidone |
| CN103706266A (en) * | 2013-12-12 | 2014-04-09 | 四川大学 | In-situ polymerization mico-crosslinking polyvinylpyrrolidone modified polyether sulfone hollow fiber membrane and preparation method and use thereof |
| CN103706266B (en) * | 2013-12-12 | 2016-01-27 | 四川大学 | In-situ polymerization micro-PVPP modified poly (ether-sulfone) hollow-fibre membrane and its production and use |
| CN105879715A (en) * | 2014-12-16 | 2016-08-24 | 天津工业大学 | Preparation method for metal organic skeleton film on polyether sulfone support |
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| JP2019508523A (en) * | 2015-12-30 | 2019-03-28 | サイテック インダストリーズ インコーポレイテッド | Surface-treated polymer particles, slurry containing the particles, and uses thereof |
| US11034795B2 (en) | 2015-12-30 | 2021-06-15 | Cytec Industries Inc. | Surface-treated polymeric particles, slurry containing the same, and use thereof |
| CN109092068A (en) * | 2018-10-08 | 2018-12-28 | 湖北中泉环保技术有限公司 | A kind of ultrafiltration membrane preparation method |
| CN111732732A (en) * | 2020-06-02 | 2020-10-02 | 上海大学 | Polyether sulfone grafted polyethylene glycol methacrylate copolymer, film and preparation method thereof |
| CN114044864A (en) * | 2021-11-17 | 2022-02-15 | 暨南大学 | Block copolymer and application thereof in preparation of ultrafiltration membrane for filtering vaccine |
| CN114044864B (en) * | 2021-11-17 | 2023-12-19 | 暨南大学 | Block copolymer and application thereof in preparation of ultrafiltration membrane for vaccine filtration |
| CN115073740A (en) * | 2022-07-19 | 2022-09-20 | 宁夏清研高分子新材料有限公司 | Polysulfone polymer and preparation method thereof |
| CN115073740B (en) * | 2022-07-19 | 2023-08-29 | 宁夏清研高分子新材料有限公司 | Polysulfone polymer and preparation method thereof |
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