CN111732732A - Polyether sulfone grafted polyethylene glycol methacrylate copolymer, film and preparation method thereof - Google Patents
Polyether sulfone grafted polyethylene glycol methacrylate copolymer, film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyether sulfone grafted polyethylene glycol methacrylate copolymer, a film and a preparation method thereof, wherein the preparation method comprises the following steps: washing and soaking the raw material polyether sulfone, and drying to constant weight; mixing the polyether sulfone obtained after drying with a polyethylene glycol methacrylate monomer to prepare a homogeneous solution, and carrying out a co-radiation grafting reaction on the polyethylene glycol methacrylate monomer and the polyether sulfone in the homogeneous solution containing the polyethylene glycol methacrylate monomer and the polyether sulfone; carrying out post-treatment on a homogeneous phase solution obtained after the co-radiation grafting reaction; and (3) performing reversed-phase precipitation on the homogeneous phase solution obtained after the co-radiation grafting reaction in deionized water, washing the obtained solid, soaking in the deionized water, and performing vacuum drying to constant weight. The invention carries out PEGMA grafting on the PES material body, can prepare graft copolymers with different grafting rates according to the needs, has more flexible application and improves the performance of the graft copolymers.
Description
Technical Field
The invention relates to a polyether sulfone grafted polyethylene glycol methyl ether methacrylate monomer copolymer, a film and a preparation method thereof, which are applied to the technical field of high polymer substrates.
Background
At present, the membrane separation technology is widely applied to the fields of petroleum industry, seawater desalination, sewage treatment, gas separation and the like, has the advantages of good separation precision, greenness, no pollution, convenience in operation and the like, and the membrane is also widely concerned as the core of the membrane separation technology. Polyether sulfone (PES) is a polymer base material which is widely used in industry and has excellent mechanical properties, the molecular structure of the PES is composed of ether groups, sulfone groups and phenylene, the ether groups endow the molecular chain of the polymer with flexibility, and the sulfone groups and the phenylene endow the polymer with excellent thermodynamic properties and processing properties. The high-temperature-resistant high-pressure-resistant high-temperature-resistant high-pressure-resistant high-temperature.
However, the development of polyethersulfone membranes has been limited by a number of problems, the greatest of which is membrane fouling. As the polyether sulfone has stronger hydrophobic property, a plurality of macromolecular proteins, colloids, oil stains and the like are adsorbed on the surface of the membrane during filtration, membrane pores are blocked, the flux is reduced, and even the membrane is damaged, so that the filtration efficiency is influenced, and the cost is increased. Structurally, the hydrophobic property of the polyethersulfone is caused by the lack of hydrophilic groups, so that other functional groups can be introduced into the polyethersulfone by a chemical modification method, so that the polarity of the polyethersulfone material can be improved, the stain resistance of the membrane can be improved, and the application field of the polyethersulfone material can be further expanded.
At present, the commonly used modification methods include physical blending, chemical grafting, ultraviolet irradiation, plasma irradiation and the like, and the methods all have the advantages and the disadvantages: such as a physical blending method, the operation is simple, but because chemical bonds are not generated and the compounds are combined together only by the action of force, the stability of a mixed product is poor; the chemical grafting method needs to add an initiator to initiate chain growth, the operation is complex and the initiator is difficult to remove; ultraviolet rays and plasma irradiation can only modify the surface of the body, but cannot modify the inside of the body.
PEGs are water-soluble high-molecular compounds with molecular chains in linear regular helical structures, and are non-toxic and low in irritation. In water, a PEG chain can form a large number of hydrogen bonds with water, and C-O bonds in the chain are more flexible than C-C bonds, so that the flexibility of the PEG chain in water is very good, the hydrophilicity of PES can be effectively improved by grafting a prepolymer containing a PEG structure on the PES, polyethylene glycol methacrylate (PEGMA) is used as a derivative of PEG, the PEG chain has excellent hydrophilicity and flexibility, and meanwhile, the PEG chain also contains a C-C bond structure, so that the grafting reaction with the PES is easier to occur. The gamma ray has strong penetrating power, the operation is convenient, the process is simple, at present, no report on the modification of PEGMA on PES by using gamma ray irradiation exists, and a thought is provided for the research of people.
At present, there is a report of ultraviolet light-induced polyethylene glycol methacrylate (PEGMA) grafting on the surface of a polyethersulfone membrane (PES membrane), and the main problems of the technology are that: on one hand, certain wave bands of ultraviolet light have obvious degradation effect on polyether sulfone and can affect the properties of the material; on the other hand, grafting is carried out on the surface of the polyether sulfone membrane, so that a grafting chain blocking the pore channel of the polyether sulfone membrane is easily formed, the size and the distribution of the membrane pore are uneven, the flux of the polyether sulfone membrane is greatly influenced, and the membrane flux is usually reduced by 50-80%. This problem is urgently needed to be solved.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide a polyether sulfone grafted polyethylene glycol methacrylate copolymer, a film and a preparation method thereof, and the polyether sulfone grafted polyethylene glycol methacrylate copolymer, the film and the preparation method thereof are provided, so that the defects that when a polyethylene glycol methacrylate (PEGMA) monomer is grafted on the surface of a polyether sulfone film (PES film) through ultraviolet light induction in the prior art, certain wave bands of ultraviolet light have obvious degradation effect on polyether sulfone and can influence the properties of materials, and grafting is performed on the surface of the polyether sulfone film, so that a grafting chain blocking a pore channel of the polyether sulfone film is easily formed, and the influence on the flux of the polyether sulfone film is large are overcome. The graft copolymer can effectively improve the polarity and the flexibility of a molecular chain; the crosslinking is not easy, and the dispersion and the solubility in a solvent are good; when the film is prepared, the film has good compatibility with a pore-forming agent, and the obtained film has good hydrophilicity. The graft rate of the graft copolymer is controlled in a specific range, so that the prepared film has reasonable proportion of the main chain and the side chain structure, and the hydrophilic groups of the side chain are uniformly distributed, so that the prepared film has better hydrophilicity.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of polyether sulfone grafted polyethylene glycol methacrylate copolymer comprises the following steps:
(1) pretreatment of raw materials:
washing and soaking the raw material polyether sulfone, and drying to constant weight; in order to remove impurities which influence grafting reaction in raw material polyether sulfone as easily as possible in the subsequent product post-treatment process, the method firstly carries out pretreatment operation;
(2) the process of the co-irradiation grafting reaction:
mixing the polyether sulfone obtained after drying in the step (1) with a polyethylene glycol methacrylate monomer to prepare a homogeneous solution, wherein the solvent of the homogeneous solution is N, N-dimethylacetamide; the mass ratio of the polyether sulfone to the polyethylene glycol methacrylate monomer is 10: 1-10: 9; in a homogeneous phase solution containing polyethylene glycol methacrylate monomer and polyether sulfone, carrying out co-radiation grafting reaction on the polyethylene glycol methacrylate monomer and the polyether sulfone;
(3) post-treatment of a grafting reaction product:
carrying out post-treatment on the homogeneous phase solution obtained after the co-radiation grafting reaction in the step (2); the post-treatment operation is carried out according to the following steps:
after the co-radiation grafting reaction, obtaining a homogeneous phase solution, performing reverse phase precipitation in deionized water, washing the obtained solid, soaking in deionized water, and performing vacuum drying to constant weight to obtain a polyether sulfone grafted polyethylene glycol methacrylate copolymer; the soaking time of the deionized water is 20-26 hours, the vacuum drying temperature is 50-80 ℃, and the vacuum degree of the vacuum drying is 0.06-0.08 MPa. The more preferable soaking time of the deionized water is 24 hours; more preferably 70 deg.C; more preferably 0.07 MPa.
In the present invention, in the step (2), if the mass ratio of the polyether sulfone to the polyethylene glycol methacrylate monomer exceeds 10: 10, the grafting rate of the product is too high, and the influence on the structure of the body is large, so that the mass ratio of the polyether sulfone to the polyethylene glycol methacrylate monomer is controlled to be 10: 1-10: 9. more preferably 10: 3-15: 7, preferably 10: 4-10: 6.
in a preferred embodiment of the present invention, in the step (1), the weight average molecular weight of the polyethersulfone is 20000 to 200000. Preferably 142000.
As a preferred technical scheme of the invention, in the step (1), in the pretreatment process, the raw material polyether sulfone is washed by deionized water, then is soaked in the deionized water for more than one week, is replaced by the deionized water in the soaking period, and then is dried in vacuum to constant weight; the temperature of the vacuum drying is 60-80 ℃; the vacuum degree of the vacuum drying is 0.06-0.08 MPa. The temperature of vacuum drying is more preferably 70 ℃; the degree of vacuum in the vacuum drying is more preferably 0.07 MPa.
As a preferable technical solution of the present invention, in the step (2), the mass percentage concentration of the polyethylene glycol methacrylate monomer in the homogeneous solution is 1 to 9%, more preferably 3 to 7%, and most preferably 4 to 6%; in order to achieve the effect of improving the production efficiency, the mass percentage concentration of the polyether sulfone in the homogeneous solution is 10-15% under the condition that the stirring of the homogeneous solution is not affected.
As a preferred technical scheme of the invention, in the step (2), the radiation source of the co-irradiation grafting reaction is a gamma-ray radiation source,the radiation source of the co-irradiation grafting reaction is60Co; the total radiation dose of the co-radiation grafting reaction is 6-30 kGy; more preferably 5 to 15 kGy; the average dosage rate of the co-irradiation grafting reaction is 1-5.00 kGy/h; more preferably 1 to 2 kGy/h; the temperature of the co-radiation grafting reaction is 20-30 ℃; more preferably 25 deg.c.
As a preferred technical solution of the present invention, in the step (2), the atmosphere of the co-irradiation grafting reaction is an oxygen-free atmosphere; the oxygen-free atmosphere is at least one gas atmosphere of nitrogen and argon. The oxygen-free atmosphere can be obtained by adopting the conventional technical means in the field, such as introducing oxygen-free atmosphere gas into the reaction system for more than 15min before radiation so as to remove oxygen in the system.
The polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer is prepared by the preparation method of the polyether sulfone grafted polyethylene glycol methacrylate copolymer.
The invention discloses a polyether sulfone grafted polyethylene glycol methacrylate copolymer film, which takes a polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer as a raw material, and the preparation method of the polyether sulfone grafted polyethylene glycol methacrylate copolymer film comprises the following steps: dissolving polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer in an organic solvent to prepare a membrane casting solution; and then, blade-coating the casting solution on a substrate, forming a film in an aqueous solution in a reverse phase manner, and curing to obtain the film. Preferably, the knife coating operation and conditions are those conventional in the art. Preferably, the blade coating operation is performed by ensuring that the casting solution is uniformly blade coated on the substrate. Preferably, the substrate may be a substrate conventional in the art for film formation, typically a glass plate.
As a preferable technical scheme, in the preparation method, the mass percentage concentration of the polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer in the membrane casting solution is 16-20%; more preferably 18%; the organic solvent in the membrane casting solution is N, N-dimethylacetamide; the film curing conditions were: curing in water at 18-25 ℃ for 46-50 h; more preferably in water at 20 ℃ for 48 h.
As the preferable technical scheme, in the preparation method, the thickness of the prepared film is 180-250 mu m; more preferably 250 μm.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. according to the invention, the PES material body is subjected to PEGMA grafting, graft copolymers with different grafting rates can be prepared according to requirements, and the application is more flexible; moreover, the PEGMA monomer can form a brush-shaped grafted polymer molecular structure on PES molecules, and the grafting rate is moderate; the performance of the graft copolymer is improved, and the polarity and the flexibility of a molecular chain can be effectively improved; the graft copolymer can effectively improve the polarity and the flexibility of a molecular chain, is not easy to crosslink, and has good dispersibility and dissolubility in a solvent;
2. when the film is prepared, the film has good compatibility with a pore-forming agent, and the obtained film has good hydrophilicity; the graft rate of the graft copolymer is controlled in a specific range, so that the prepared film has reasonable proportion of the main chain and side chain structures and uniform distribution of hydrophilic groups of the side chains, and has better hydrophilicity;
3. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
FIG. 1 is an infrared spectrum of a product obtained in the first embodiment of the present invention.
FIG. 2 is an infrared spectrum of a product obtained in example two of the present invention.
FIG. 3 is an infrared spectrum of a product obtained in example III of the present invention.
FIG. 4 is an IR spectrum of a product obtained in example four of the present invention.
FIG. 5 is an infrared spectrum of a product obtained by comparative example of the present invention.
FIG. 6 is an analysis chart of the result of detecting the static water contact angle of the film obtained in example five of the present invention.
FIG. 7 is a graph showing the results of pure water flux measurement of the film obtained in example five of the present invention.
FIG. 8 is a graph showing the results of analyzing the performance of membrane-filtered Bovine Serum Albumin (BSA) obtained in example five of the present invention.
FIG. 9 is a graph showing the anti-contamination effect detection analysis of the pure water recovery rate of the film obtained in example V of the present invention.
Detailed Description
In the following examples and comparative examples, N, N-dimethylacetamide was analytically pure and purchased from the national institutes of medicine. Polyether sulfone (PES) in examples one to five and comparative examples was 049, purchased from rainbow high and new materials (laiyang) ltd, having a weight average molecular weight of 14.2 ten thousand, and subjected to the following pretreatment operations before being subjected to the irradiation reaction: washing raw material polyether sulfone with deionized water, soaking in the deionized water for more than one week, replacing the deionized water for many times, and vacuum-drying the raw material polyether sulfone to constant weight under the conditions of 70 ℃ and 0.07MPa of vacuum degree by using a vacuum drying oven to obtain polyether sulfone (PES) powder serving as a pretreated raw material.
The above scheme is further illustrated below with reference to specific examples, which are detailed below for preferred embodiments of the present invention:
the first embodiment is as follows:
in this embodiment, a method for preparing a polyethersulfone grafted polyethylene glycol methacrylate copolymer includes the following steps:
a. the process of the co-irradiation grafting reaction:
weighing 10g of pretreated polyether sulfone (PES) powder, dissolving the powder in 89g of DMAc solvent, adding 1g of polyethylene glycol methacrylate monomer (PEGMA) monomer, stirring for 24h to obtain a reactant homogeneous solution, introducing N2Standing for more than 15min, and standing the homogeneous solution60COCarrying out co-radiation reaction at 25 ℃ under a source, wherein the radiation dose rate is 1.67kGy/h, and the total radiation dose of the co-radiation grafting reaction is 10 kGy;
b. post-treatment of a grafting reaction product:
after the irradiation reaction is finished, post-treating the homogeneous phase solution obtained after the co-irradiation grafting reaction in the step a; the post-treatment operation is carried out according to the following steps:
and (2) performing a co-radiation grafting reaction to obtain a homogeneous solution, performing reverse phase precipitation in deionized water, washing the obtained solid, soaking the washed solid in deionized water for 24 hours, pouring the deionized water, and performing vacuum drying on the obtained solid in a vacuum oven under the conditions of 70 ℃ and 0.07MPa of vacuum degree to constant weight to obtain the polyether sulfone grafted polyethylene glycol methacrylate copolymer.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for preparing a polyethersulfone grafted polyethylene glycol methacrylate copolymer includes the following steps:
a. the process of the co-irradiation grafting reaction:
weighing 10g of pretreated polyether sulfone (PES) powder, dissolving the powder in 85g of DMAc solvent, adding 5g of polyethylene glycol methacrylate monomer (PEGMA) monomer, stirring for 24h to obtain a reactant homogeneous solution, introducing N2Standing for more than 15min, and standing the homogeneous solution60COCarrying out co-radiation reaction at 25 ℃ under a source, wherein the radiation dose rate is 1.67kGy/h, and the total radiation dose of the co-radiation grafting reaction is 10 kGy;
b. the procedure is the same as in the first embodiment.
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing a polyethersulfone grafted polyethylene glycol methacrylate copolymer includes the following steps:
a. the process of the co-irradiation grafting reaction:
weighing 10g of pretreated polyether sulfone (PES) powder, dissolving the powder in 81g of DMAc solvent, adding 9g of polyethylene glycol methacrylate monomer (PEGMA) monomer, and stirring for 24h to obtain a reactant homogeneous phaseSolution, passing through N2Standing for more than 15min, and standing the homogeneous solution60COCarrying out co-radiation reaction at 25 ℃ under a source, wherein the radiation dose rate is 1.67kGy/h, and the total radiation dose of the co-radiation grafting reaction is 10 kGy;
b. the procedure is the same as in the first embodiment.
Example four:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing a polyethersulfone grafted polyethylene glycol methacrylate copolymer includes the following steps:
a. the process of the co-irradiation grafting reaction:
weighing 10g of pretreated polyether sulfone (PES) powder, dissolving the powder in 81g of DMAc solvent, adding 9g of polyethylene glycol methacrylate monomer (PEGMA) monomer, stirring for 24h to obtain a reactant homogeneous solution, introducing N2Standing for more than 15min, and standing the homogeneous solution60COCarrying out co-radiation reaction at 25 ℃ under a source, wherein the radiation dose rate is 1kGy/h, and the total radiation dose of the co-radiation grafting reaction is 6 kGy;
b. the procedure is the same as in the first embodiment.
Comparative example
Accurately weighing 10g of pretreated PES powder, dissolving the PES powder in 90g of DMAc solvent, stirring for 24h to obtain a homogeneous solution, introducing N2Standing for more than 15min, and standing the homogeneous solution60CORadiation was carried out at 25 ℃ under a source at a dose rate of 1.67kGy/h and an absorbed dose of 10 kGy.
After the irradiation, the resulting solution was subjected to a post-treatment operation, which was identical to the operation and conditions of example one.
Example five:
in this example, the polyethersulfone grafted polyethylene glycol methacrylate copolymer products obtained in the first to third examples and the comparative example are respectively used to prepare corresponding membranes, and the membrane preparation method comprises the following steps: dissolving polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer in an N, N-dimethylacetamide organic solvent to prepare a membrane casting solution, wherein the mass percentage concentration of the polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer in the membrane casting solution is 18%; and then coating the casting solution on a substrate, performing reverse phase film formation in an aqueous solution, and curing in 18 ℃ water for 24 hours to respectively obtain corresponding polyether sulfone grafted polyethylene glycol methacrylate copolymer films, wherein the film thickness is 250 micrometers.
Experimental test analysis:
firstly, detecting the grafting effect by adopting a Fourier infrared light instrument:
FT-IR tests were carried out on the products obtained in examples one to four and comparative example as samples, and the results are shown in FIGS. 1 to 5.
FT-IR test: respectively drying the products of the first to fourth examples and the comparative example, grinding the dried products into powder, preparing into potassium bromide tablets, placing the potassium bromide tablets into a Fourier infrared spectrometer, model NICOLEVATAR-370, scanning the transmission spectrum of a sample by adopting an ATR mode, wherein the scanning range is 4000-400 CM-1And the number of scanning times is 32.
FIGS. 1 to 4 are infrared spectrograms of the products obtained in the first to fourth examples in this order. FIG. 5 is an IR spectrum of a product obtained in the comparative example. As can be seen from FIG. 5, the length of the hole is 848cm-1、740cm-1The peaks at the left and right are out-of-plane stretching vibration peaks of C-H bonds on benzene rings; at 1150cm-1The left and right peaks are SO2The stretching vibration peak in the symmetrical plane; and at 1240cm-1The left and right peaks are stretching vibration peaks in a symmetrical plane of the ether group C-O; at 1578cm-1、1486cm-1The peak of (b) corresponds to bending vibration of the entire benzene ring. Compared with the graph of fig. 5, the main difference of the graft modified copolymer of polyether sulfone grafted polyethylene glycol methacrylate monomer shown in fig. 1-4 is that the graft modified copolymer is positioned at 1720cm-1A new absorption peak appears around, which is the absorption vibration peak of carbonyl group C ═ O on the grafted monomer. Furthermore, as can be seen from fig. 1 to 3, the absorption peak at the position appears to be obviously increased with the increasing concentration of the monomer (PEGMA), which shows that the grafting rate is increased with the increasing concentration of the monomer, and proves the reaction effectiveness of the graft copolymer and the linear relationship of the grafting rate with the increasing concentration.
Secondly, detecting the static water contact angle of the film:
the contact angles of examples one to three and comparative examples were measured by an attention Theta System, the contact angle measurement method being conventional in the art and generally being performed as follows: 5 mul of deionized water was dropped onto the membrane surface with a needle, the magnified drop image was collected, the contact angle was calculated by the corresponding procedure, and the average of the three measurements was taken. Specific data of the contact angle are shown in fig. 6, and specific data of the contact angle are shown in table 1. As can be seen from fig. 6, the static water contact angle of the membrane becomes smaller and smaller as the concentration of the graft monomer increases, indicating that the hydrophilicity of the membrane becomes better and better.
TABLE 1 specific data table for contact angles of products prepared in examples one to three and comparative examples
Third, the pure water flux of the film is detected
The pure water flux of the film obtained in example five, that is, the pure water flux of the films prepared from the products obtained in examples one to three and comparative example, respectively, as raw materials, was measured. The pure water capacity of the three films obtained in example five were measured as follows:
(1) the film obtained in example five was cut into an area of 35.3cm2The round film is placed in a film pressing component of a film flux tester, and the film is compacted for 20min by deionized water when the pressure is 0.01 MPa;
(2) when the pure water flux of the film is detected, the pure water is filtered by the film under 0.01MPa, and the pure water flux of the film is obtained from the software of the film flux tester.
FIG. 7 is a graph showing the results of pure water flux measurement of the film obtained in example V. The specific data are shown in Table 2. As can be seen from fig. 7, the pure water flux of the membranes corresponding to the products obtained in the first to third examples is much larger than that of the membrane prepared from the polyether sulfone material without graft modification in the comparative example. Moreover, the higher the graft monomer concentration, the more significant the increase in pure water flux of the film. After PES is modified by a plurality of small molecules, the water flux is reduced with the increase of the grafting rate, for example, in patent CN107641178A, the pure water flux of the modified film is reduced; similarly, the water flux decreases with increasing grafting yield after modification of PES with PMAA. Therefore, the pure water flux modified by the method is obviously increased along with the increase of the grafting rate, so that the method can improve the filtration efficiency and save the capacity in industrial application, and has important significance.
TABLE 2 results of measurement of pure water flux of thin films prepared from the products of examples one to three and comparative example, respectively
Fourthly, performance test analysis of membrane filtration Bovine Serum Albumin (BSA):
analyzing the membrane-filtered bovine serum albumin obtained in the fifth example, and evaluating the filtering performance; namely, bovine serum albumin was filtered through membranes prepared from the products obtained in examples one to three and comparative examples, respectively, and the filtration performance was evaluated. The detection method comprises the following steps:
(1) preparing 1L of phosphate buffer solution, adjusting the pH value to 7.4, adding 1g of bovine serum albumin to prepare a bovine serum albumin solution, namely BSA solution for short, wherein Mw is 20000 and 500 ppm;
(2) the film of example 5 was cut to an area of about 35.3cm2The circular thin film is put into a membrane flux measuring instrument, BSA solution flows back in the membrane flux measuring instrument at the speed of 2kg/h, the pressure of the membrane flux measuring instrument is adjusted to be 0.01MPa, the filtration operation is carried out, the medium flux is obtained by the membrane flux measuring instrument, and the liquid after membrane filtration is taken from the filtrate outlet of the membrane flux measuring instrument;
(3) and (3) obtaining the BSA content in the solution before and after filtration by using an ultraviolet spectrophotometer, thereby calculating the rejection rate of the membrane.
FIG. 8 shows the retention of the films obtained in example IV at different concentrations of the graft monomer, the data being shown in Table 3. As can be seen from fig. 8, the retention rates of the products obtained in the first to third examples are not greatly changed compared with the unmodified pure polyethersulfone membrane, and the retention rates are all above 90%. Therefore, the film product prepared by the grafting product has better filtering performance.
TABLE 3 Retention Rate data of membranes at different graft monomer concentrations
Fifthly, detecting and analyzing the pure water recovery rate of the film, namely the anti-pollution effect:
the film obtained in example five was analyzed to evaluate its filtration performance. Namely, the filtration performance of each of the membranes prepared from the products obtained in examples one to three and comparative examples was evaluated. The detection method comprises the following steps:
(1) the film of example five was cut to an area of about 35.3cm2The round thin film is put into a membrane flux tester, and pure water is used for compacting for half an hour under the pressure of 0.1MPa and the flow rate of 2kg/h, and then the pure water flux is obtained from the flux tester;
(2) preparing 1L of phosphate buffer solution, adjusting the pH value to 7.4, adding 1g of bovine serum albumin to prepare a bovine serum albumin solution, namely BSA solution for short, wherein Mw is 20000 and 500 ppm;
(3) replacing the reflux liquid of a flux tester with BSA solution, and filtering the BSA solution by a membrane for half an hour at the speed of 2kg/h and the pressure of 0.1 MPa;
(4) changing the reflux liquid of the membrane flux tester into pure water, wherein the flow rate is 5kg/h, the pressure is 0MPa, and the reflux liquid can reach the effect of cleaning the surface of the membrane when the reflux liquid is half;
(5) the pure water after washing was replaced, and the pure water flux for the second time was measured at a speed of 2kg/h and a pressure of 0.1 MPa.
FIG. 9 shows pure water, medium flux and pure water recovery for membranes prepared according to the different concentrations of the graft monomer obtained in example five, and the specific data are shown in Table 4. The pure water flux and the medium flux of the grafted membrane are obviously increased, and the pure water recovery rate is very high, which shows that the anti-pollution effect of the modified membrane is very good.
TABLE 4 data sheet for pure water, media flux and pure water recovery for membranes prepared with different graft monomer concentrations
In conclusion, the graft copolymer can effectively improve the polarity and the flexibility of a molecular chain, is not easy to crosslink, and has good dispersibility and dissolubility in a solvent; when the film is prepared, the film has good compatibility with a pore-forming agent, and the obtained film has good hydrophilicity. The graft rate of the graft copolymer is controlled in a specific range, so that the prepared film has reasonable proportion of the main chain and the side chain structure and uniform distribution of the side chain hydrophilic groups, and has better hydrophilicity. The invention carries out PEGMA grafting on the PES material body, can prepare graft copolymers with different grafting rates according to the needs, has more flexible application and improves the performance of the graft copolymers.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical scheme of the present invention shall be equivalent substitution patterns, so long as the object of the present invention is met, and the polyethersulfone grafted polyethyleneglycol methacrylate copolymer, the film and the method for preparing the same shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (10)
1. The preparation method of the polyether sulfone grafted polyethylene glycol methacrylate copolymer is characterized by comprising the following steps:
(1) pretreatment of raw materials:
washing and soaking the raw material polyether sulfone, and drying to constant weight;
(2) the process of the co-irradiation grafting reaction:
mixing the polyether sulfone obtained after drying in the step (1) with a polyethylene glycol methacrylate monomer to prepare a homogeneous solution, wherein the solvent of the homogeneous solution is N, N-dimethylacetamide; the mass ratio of the polyether sulfone to the polyethylene glycol methacrylate monomer is 10: 1-10: 9; in a homogeneous phase solution containing polyethylene glycol methacrylate monomer and polyether sulfone, carrying out co-radiation grafting reaction on the polyethylene glycol methacrylate monomer and the polyether sulfone;
(3) post-treatment of a grafting reaction product:
carrying out post-treatment on the homogeneous phase solution obtained after the co-radiation grafting reaction in the step (2); the post-treatment operation is carried out according to the following steps:
after the co-radiation grafting reaction, obtaining a homogeneous phase solution, performing reverse phase precipitation in deionized water, washing the obtained solid, soaking in deionized water, and performing vacuum drying to constant weight to obtain a polyether sulfone grafted polyethylene glycol methacrylate copolymer; the soaking time of the deionized water is 20-26 hours, the vacuum drying temperature is 50-80 ℃, and the vacuum degree of the vacuum drying is 0.06-0.08 MPa.
2. The method for preparing the polyether sulfone grafted polyethylene glycol methacrylate copolymer according to claim 1, which is characterized in that: in the step (1), the weight average molecular weight of the polyether sulfone is 20000-200000.
3. The method for preparing the polyether sulfone grafted polyethylene glycol methacrylate copolymer according to claim 2, which is characterized in that: in the step (1), in the pretreatment process, the raw material polyether sulfone is washed by deionized water, then is soaked in the deionized water for more than one week, the deionized water is replaced during the soaking, and then is dried in vacuum to constant weight; the temperature of the vacuum drying is 60-80 ℃; the vacuum degree of the vacuum drying is 0.06-0.08 MPa.
4. The method for preparing the polyether sulfone grafted polyethylene glycol methacrylate copolymer according to claim 1, which is characterized in that: in the step (2), the mass percentage concentration of the polyethylene glycol methacrylate monomer in the homogeneous solution is 1-9%; the mass percentage concentration of the polyether sulfone in the homogeneous solution is 10-15%.
5. The method for preparing the polyether sulfone grafted polyethylene glycol methacrylate copolymer according to claim 1, which is characterized in that: in the step (2), the radiation source of the co-irradiation grafting reaction is60Co; the total radiation dose of the co-radiation grafting reaction is 6-30 kGy; the average dosage rate of the co-irradiation grafting reaction is 1-5.00 kGy/h; the temperature of the co-radiation grafting reaction is 20-30 ℃.
6. The method for preparing the polyether sulfone grafted polyethylene glycol methacrylate copolymer according to the claim 1, wherein in the step (2), the atmosphere of the co-irradiation grafting reaction is an oxygen-free atmosphere; the oxygen-free atmosphere is at least one gas atmosphere of nitrogen and argon.
7. A polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer prepared by the preparation method of the polyether sulfone grafted polyethylene glycol methacrylate copolymer as described in any one of claims 1-6.
8. A polyether sulfone grafted polyethylene glycol methacrylate copolymer film takes the polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer as claimed in claim 7 as a raw material, and is characterized in that the preparation method of the polyether sulfone grafted polyethylene glycol methacrylate copolymer film comprises the following steps: dissolving polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer in an organic solvent to prepare a membrane casting solution; and then, blade-coating the casting solution on a substrate, forming a film in an aqueous solution in a reverse phase manner, and curing to obtain the film.
9. The polyethersulfone-grafted polyethylene glycol methacrylate copolymer membrane of claim 8, wherein: in the preparation method, the mass percentage concentration of the polyether sulfone grafted polyethylene glycol methacrylate monomer copolymer in the membrane casting solution is 16-20%; the organic solvent in the membrane casting solution is N, N-dimethylacetamide; the film curing conditions were: curing the mixture in water at 18-25 ℃ for 46-50 h.
10. The polyethersulfone-grafted polyethylene glycol methacrylate copolymer membrane of claim 8, wherein: in the preparation method, the thickness of the prepared film is 180-250 mu m.
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