CN103157388A - Hydrophilic reverse osmosis composite membrane and preparation method thereof - Google Patents
Hydrophilic reverse osmosis composite membrane and preparation method thereof Download PDFInfo
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- CN103157388A CN103157388A CN2013100865736A CN201310086573A CN103157388A CN 103157388 A CN103157388 A CN 103157388A CN 2013100865736 A CN2013100865736 A CN 2013100865736A CN 201310086573 A CN201310086573 A CN 201310086573A CN 103157388 A CN103157388 A CN 103157388A
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Abstract
The invention relates to a hydrophilic reverse osmosis composite membrane and a preparation method of the hydrophilic reverse osmosis composite membrane, which relates to the field of membrane separation. In order to solve the problems of poor hydrophilicity and low pollution resistance of the existing reverse osmosis composite membrane prepared by metaphenylene diamine and trimesic acyl chloride, the invention provides the hydrophilic reverse osmosis composite membrane with strong hydrophilicity and pollution resistance and high salt rejection rate and water flux and the preparation method of the hydrophilic reverse osmosis composite membrane. The hydrophilic reverse osmosis composite membrane comprises a porous polysulfone supporting layer, an active separating layer and a hydrophilic coating layer, wherein the molecular weight cut-off of the porous polysulfone supporting layer is 20000-50000; the active separating layer is composited on the surface of the porous polysulfone supporting layer and is a polymer obtained by metaphenylene diamine and biphenyl multielement acyl chloride through interfacial polymerization; and the hydrophilic coating layer is coated on the surface of the active separating layer and is a hydrophilic polymer. The hydrophilic reverse osmosis composite membrane has the advantages that the hydrophilicity is strong, the pollution resistance is strong, the desalting rate reaches to be 99.83%, the water flux reaches to be 56.8L/m<2>h, and the comprehensive performance is obviously improved.
Description
Technical field
The present invention relates to the membrane separation technique field, be specifically related to a kind of hydrophily reverse osmosis composite membrane and preparation method thereof.
Background technology
Reverse osmosis membrane is that a class adopts Polymer materialspreparation, can realize the artificial pellicle that reverse osmosis membrane separation operates, it is high that it has salt rejection rate, mechanical strength is high, long service life, and the masking raw material easily obtains, process easy, with low cost, affected by the factors such as pH value and temperature less, can be than bringing into play function under low operating pressure, and can tolerate the advantages such as chemistry or biochemical action impact, be widely used in the various fields such as chemical industry, water treatment, desalinization, medicine.
Reverse osmosis membrane comprises two large classes: the first kind is the cellulose acetate series membranes with unsymmetric structure, and this class film requires higher due to its pH narrow application range, facile hydrolysis, operating pressure and the reason such as water flux is lower, and its development is restricted; Equations of The Second Kind is the aromatic polyamide reverse osmosis composite membrane, and this class film has that salt rejection rate is high, water flux is large, the pH scope of application is wide and have preferably the advantage such as chemical stability, is widely used.
at present, the aromatic polyamide reverse osmosis composite membrane is mainly prepared by interfacial polymerization by m-phenylene diamine (MPD) and trimesoyl chloride, the aromatic polyamide reverse osmosis composite membrane that is prepared by interfacial polymerization by m-phenylene diamine (MPD) and trimesoyl chloride, in preparation process, the polymerisation of m-phenylene diamine (MPD) and trimesoyl chloride generation amido and acid chloride groups, also be accompanied by simultaneously the hydrolysis of acid chloride groups, the hydrophily of composite membrane mainly is hydrolyzed into carboxylic acid by residual acid chloride groups and provides, acid chloride groups limited amount due to the composite membrane remained on surface, cause the composite membrane hydrophily poor, contamination resistance descends, if reduce the content of m-phenylene diamine (MPD), a small amount of acid chloride groups and amido are reacted, can improve the content of the acid chloride groups of composite membrane remained on surface, the hydrophily of composite membrane also increases, but can not guarantee that again composite membrane has the suitable degree of cross linking, this will cause the salt rejection of composite membrane to descend, if at composite membrane surface coating last layer hydrophilic polymer, the acid chloride groups generation covalence graft modification of hydrophilic polymer and composite membrane remained on surface, hydrophilic polymer is brushed in the composite membrane finishing thus, can improve hydrophily and the antifouling property of composite membrane, but, acid chloride groups limited amount due to the composite membrane remained on surface, cause the quantity of hydrophilic polymer brush of surperficial covalence graft also limited, can't form fine and close hydrophilic coating, cause the composite membrane hydrophily poor, contamination resistance reduces, if adopt the method for physics coating at composite membrane surface coating last layer hydrophilic coating, because the interaction force between hydrophilic coating and composite membrane is poor, long-term use easily causes hydrophilic coating to come off from the composite membrane surface, make composite membrane lose the hydrophilic modifying effect, hydrophily and contamination resistance descend, and water flux decreases, when at composite membrane surface coating hydrophilic polymer, be difficult to control coated weight, coated weight is many, causes water resistance to increase, the water flux reduction, coated weight has lacked, and hydrophilic polymer easily in use runs off, and causes the hydrophily of composite membrane and contamination resistance to reduce.
Summary of the invention
In order to solve the existing problem that hydrophily is poor, contamination resistance is low that is existed by the reverse osmosis composite membrane of m-phenylene diamine (MPD) and trimesoyl chloride preparation, the invention provides that a kind of hydrophily is strong, contamination resistance strong, salt rejection and the high hydrophily reverse osmosis composite membrane of water flux and preparation method thereof.
The present invention is that the technical scheme that adopts of technical solution problem is as follows:
A kind of hydrophily reverse osmosis composite membrane, this composite membrane comprises:
Molecular cut off is 20000～50000 porous polysulfone supporting layer;
Be compound in the active separating layer on described porous polysulfone supporting layer surface, the polymer of described active separating layer for being obtained by interfacial polymerization by m-phenylene diamine (MPD) and the polynary acyl chlorides of biphenyl;
Be coated on the hydrophilic coating on described active separating layer surface, described hydrophilic coating is hydrophilic polymer.
The polynary acyl chlorides of described biphenyl is 2,2 ', 4,4 '-biphenyl four acyl chlorides, 2,2 ', 5,5 '-biphenyl four acyl chlorides, 3,3 ', 5,5 '-biphenyl four acyl chlorides, 2,3 ', 4,5 ', 6 ,-biphenyl five acyl chlorides or 2,2 ', 4,4 ', 6,6 '-biphenyl six acyl chlorides;
Described 2,2 ', 4,4 '-structural formula of biphenyl four acyl chlorides is:
Described 2,2 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
Described 3,3 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
Described 2,3 ', 4,5 ', 6, the structural formula of-biphenyl five acyl chlorides is:
Described 2,2 ', 4,4 ', 6,6 '-structural formula of biphenyl six acyl chlorides is:
Described hydrophilic polymer is that PEG400, Macrogol 2000, molecular weight are 400～20000 polyvinyl alcohol or the PEG400 of amido end-blocking.
The preparation method of a kind of hydrophily reverse osmosis composite membrane of the present invention, condition and the step of the method are as follows:
Step 1, be that molecular cut off that the aqueous solution of the m-phenylene diamine (MPD) of 1.5g/100mL～3g/100mL evenly is poured over hygrometric state is 20000～50000 porous polysulfone supporting layer surface with the mass body volume concentrations, obtain the porous polysulfone supporting layer that surface coverage has m-phenylene diamine (MPD);
Step 2, be that the IsopaG of the polynary acyl chlorides of biphenyl of 0.05g/100mL～0.2g/100mL and the mixed solution of toluene evenly are poured over the porous polysulfone supporting layer surface that obtains in step 1 with the mass body volume concentrations, carry out interface polymerization reaction, obtain the composite membrane that surface coverage has active separating layer;
Step 3, the composite membrane that obtains in step 2 is heat-treated, heated 2～7 minutes under 50 ℃～90 ℃;
Step 4, the acetone soln single face that is the hydrophilic polymer of 0.01g/100mL～1g/100mL with the composite membrane after Overheating Treatment in step 3 and mass body volume concentrations contact, rinse out the hydrophilic polymer of composite membrane surface physics absorption with deionized water, obtain the hydrophily reverse osmosis composite membrane by the hydrophilic polymer covalence graft.
The polynary acyl chlorides of described biphenyl is 2,2 ', 4,4 '-biphenyl four acyl chlorides, 2,2 ', 5,5 '-biphenyl four acyl chlorides, 3,3 ', 5,5 '-biphenyl four acyl chlorides, 2,3 ', 4,5 ', 6 ,-biphenyl five acyl chlorides or 2,2 ', 4,4 ', 6,6 '-biphenyl six acyl chlorides;
Described 2,2 ', 4,4 '-structural formula of biphenyl four acyl chlorides is:
Described 2,2 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
Described 3,3 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
Described 2,3 ', 4,5 ', 6, the structural formula of-biphenyl five acyl chlorides is:
Described 2,2 ', 4,4 ', 6,6 '-structural formula of biphenyl six acyl chlorides is:
Described active separating layer is for being the polymer that the m-phenylene diamine (MPD) of 1.5g/100mL～3g/100mL and the polynary acyl chlorides of biphenyl that the mass body volume concentrations is 0.05g/100mL～0.2g/100mL obtain by interfacial polymerization by the mass body volume concentrations.
Described hydrophilic polymer is that PEG400, Macrogol 2000, molecular weight are 400～20000 polyvinyl alcohol or the PEG400 of amido end-blocking.
The mass body volume concentrations of described m-phenylene diamine (MPD) is 2.0g/100mL.
The mass body volume concentrations of the polynary acyl chlorides of described biphenyl is 0.2g/100mL.
The mass body volume concentrations of described hydrophilic polymer is 0.5g/100mL.
The invention has the beneficial effects as follows: compared with prior art, the present invention is from the polymerization single polymerization monomer structural design, take the polynary acyl chlorides of biphenyl as polymerization single polymerization monomer, in the more acid chloride groups of reverse osmosis composite membrane surface introducing, improve the content of the surperficial covalence graft hydrophilic polymer of composite membrane;
1, the present invention utilizes the polynary acyl chlorides of biphenyl to contain than the more acid chloride groups of commercial trimesoyl chloride, guaranteeing the suitable degree of cross linking, namely guarantee under the prerequisite of composite membrane salt rejection, guarantee a large amount of acid chloride groups of composite membrane remained on surface, the hydrophilic polymer that has antipollution effect for follow-up surperficial covalence graft provides enough tie points, when improving contamination resistance, guarantees that composite membrane has higher salt rejection rate, salt rejection rate has reached 99.83%, satisfies the long-term requirement of using;
2, after the polynary acyl chlorides generation of m-phenylene diamine (MPD) and biphenyl interface polymerization reaction, the acid chloride groups that the composite membrane remained on surface is a large amount of, surperficial covalence graft effect can occur with the hydrophilic polymer that end group is amido or hydroxyl in it, and then at the fine and close hydrophilic coating of composite membrane surface formation, the method of covalence graft hydrophilic coating, improved the stability of hydrophilic coating, improved hydrophily and the contamination resistance of composite membrane, the combination property of composite membrane significantly improves;
3, the hydrophilic polymer that is amido or hydroxyl due to end group is connected with composite membrane by covalent bond, and therefore, composite membrane is when long-term the use, and hydrophilic polymer is difficult for running off; The hydrophilic polymer with composite membrane formation covalent bond can simply not wash, therefore, can accurately control the thickness of composite membrane surface hydrophilic coating, avoided because the water flux that excessive coating hydrophilic polymer causes descends, the water flux of reverse osmosis composite membrane of the present invention has reached 56.8L/m
2h。
4, preparation method's operating process of reverse osmosis composite membrane of the present invention is simple and convenient, and mild condition is fit to large-scale production.
The specific embodiment
A kind of hydrophily reverse osmosis composite membrane of the present invention, this composite membrane comprises three layers: ground floor is that molecular cut off is 20000～50000 porous polysulfone supporting layer, and the second layer is active separating layer, and the 3rd layer is hydrophilic coating; The molecular cut off of porous polysulfone supporting layer is preferably 20000～50000, the polymer of active separating layer for being obtained by interfacial polymerization by m-phenylene diamine (MPD) and the polynary acyl chlorides of biphenyl, and hydrophilic coating is hydrophilic polymer, the preparation method of this composite membrane is as follows:
Step 1, be that molecular cut off that the aqueous solution of the m-phenylene diamine (MPD) of 1.5g/100mL～3g/100mL evenly is poured over hygrometric state is 20000～50000 porous polysulfone supporting layer surface with the mass body volume concentrations, cover 1～3 minute, preferred 1 minute, topple over and remove the unnecessary aqueous solution that contains m-phenylene diamine (MPD), air dried 1～3 minute, preferred 1 minute, obtain the porous polysulfone supporting layer that surface coverage has the m-phenylene diamine (MPD) aqueous solution; The mass body volume concentrations of m-phenylene diamine (MPD) is preferably 2.0g/100mL;
Step 2, be that the IsopaG of the polynary acyl chlorides of biphenyl of 0.05g/100mL～0.2g/100mL and the mixed solution of toluene evenly are poured over the porous polysulfone supporting layer surface that obtains in step 1 with the mass body volume concentrations, carry out interface polymerization reaction 20 seconds, and obtained the composite membrane that surface coverage has active separating layer; The mass body volume concentrations of the polynary acyl chlorides of biphenyl is preferably 0.2g/100mL;
Step 3, the composite membrane that obtains in step 2 is carried out heat treatment for the first time, heated 2～7 minutes under 50 ℃～90 ℃, heating is 4 minutes under preferred 70 ℃;
step 4, the acetone soln single face in 20 ℃～40 ℃ temperature ranges that is the hydrophilic polymer of 0.01g/100mL～1g/100mL through the composite membrane after heat treatment for the first time and mass body volume concentrations in step 3 is contacted 0.5～2 minute, preferred 40 ℃ of lower single face contacts 1 minute, then be rinsing 30 minutes in the deionized water of 50 ℃ in temperature, rinse out the hydrophilic polymer of composite membrane surface physics absorption, carry out immediately heat treatment for the second time, heated 2～7 minutes under 50 ℃～90 ℃, under preferred 80 ℃, heating is 5 minutes, obtain the hydrophily reverse osmosis composite membrane of hydrophilic polymer covalence graft, the mass body volume concentrations of hydrophilic polymer is preferably 0.5g/100mL.
The polynary acyl chlorides of biphenyl in present embodiment can be selected from following any one in several, be 2,2 ' and, 4,4 '-biphenyl four acyl chlorides, 2,2 ', 5,5 '-biphenyl four acyl chlorides, 3,3 ', 5,5 '-biphenyl four acyl chlorides, 2,3 ', 4,5 ', 6,-biphenyl five acyl chlorides and 2,2 ', 4,4 ', 6,6 '-biphenyl six acyl chlorides;
2,2 ', 4,4 '-structural formula of biphenyl four acyl chlorides is:
2,2 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
3,3 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
2,3 ', 4,5 ', 6, the structural formula of-biphenyl five acyl chlorides is:
2,2 ', 4,4 ', 6,6 '-structural formula of biphenyl six acyl chlorides is:
In present embodiment, by m-phenylene diamine (MPD) and 2,2 ', 4,4 '-biphenyl four acyl chlorides are as follows by the structural formula of the polymer that interfacial polymerization prepares:
Hydrophilic polymer in present embodiment is that PEG400, Macrogol 2000, molecular weight are 400～20000 polyvinyl alcohol or the PEG400 of amido end-blocking.
The preparation process of the porous polysulfone supporting layer in present embodiment is as follows:
Prepare according to conventional method, to contain the 18.5%(percentage by weight) polysulfones, 11.5%(percentage by weight) glycol monoethyl ether, 0.03%(percentage by weight) dodecyl sodium sulfate, 66.97%(percentage by weight) N, the casting solution of dinethylformamide is coated with to be scraped on polyester non-woven fabric, under room temperature, it is immersed in and carries out inversion of phases in deionized water, remove good solvent, obtain molecular cut off and be 20000～50000 porous polysulfone supporting layer, be stored in deionized water it stand-by.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1 by m-phenylene diamine (MPD) and 2,2 ', 5,5 '-biphenyl four acyl chlorides prepare the reverse osmosis composite membrane of surperficial covalence graft Macrogol 2000
Step 1, be that molecular cut off that the aqueous solution of the m-phenylene diamine (MPD) of 2.0g/100mL evenly is poured over hygrometric state is 20000 porous polysulfone supporting layer surface with the mass body volume concentrations, cover 1 minute, topple over and remove unnecessary amine liquid, air dried 1 minute, obtained the porous polysulfone supporting layer that surface coverage has the m-phenylene diamine (MPD) aqueous solution;
Step 2, be 2 of 0.2g/100mL with the mass body volume concentrations, 2 ', 5,5 '-IsopaG of biphenyl four acyl chlorides and the mixed solution of toluene evenly be poured over the porous polysulfone supporting layer surface that obtains in step 1, carry out interface polymerization reaction 20 seconds, and obtained the composite membrane that surface coverage has active separating layer;
Step 3, the composite membrane that obtains in step 2 is carried out heat treatment for the first time, heating is 4 minutes under 70 ℃;
Step 4, acetone soln contacts 1 minute at 40 ℃ of lower single faces with being the Macrogol 2000 of 0.5g/100mL through the composite membrane after heat treatment for the first time and mass body volume concentrations in step 3, then be rinsing 30 minutes in the deionized water of 50 ℃ in temperature, rinse out the Macrogol 2000 of composite membrane surface physics absorption, carry out immediately heat treatment for the second time, under 80 ℃, heating is 5 minutes, obtain the hydrophily reverse osmosis composite membrane of covalence graft, this reverse osmosis composite membrane is kept in the deionized water of 0～5 ℃ stand-by.
Comparative example 1 is by m-phenylene diamine (MPD) and the surperficial not reverse osmosis composite membrane of covalence graft hydrophilic polymer of trimesoyl chloride preparation
Step 1, be that molecular cut off that the aqueous solution of the m-phenylene diamine (MPD) of 2.0g/100mL evenly is poured over hygrometric state is 20000 porous polysulfone supporting layer surface with the mass body volume concentrations, cover time is 1 minute, topple over and remove unnecessary amine liquid, air dried 1 minute, obtained the porous polysulfone supporting layer that surface coverage has the m-phenylene diamine (MPD) aqueous solution;
Step 2, be that the IsopaG solution of the trimesoyl chloride of 0.2g/100mL evenly is poured over the porous polysulfone supporting layer surface that obtains in step 1 with the mass body volume concentrations, carried out interface polymerization reaction 20 seconds, obtain the composite membrane that surface coverage has active separating layer;
Step 3, the composite membrane that obtains in step 2 is carried out heat treatment for the first time, heating is 4 minutes under 70 ℃; Step 4, the aqueous sodium carbonate that is 0.6g/100mL with the mass body volume concentrations are poured in step 3 through the surface of the composite membrane after heat treatment for the first time, cover 1 minute, then be rinsing 30 minutes in the deionized water of 50 ℃ in temperature, carry out immediately heat treatment for the second time, under 80 ℃, heating is 5 minutes, obtain reverse osmosis composite membrane, this reverse osmosis composite membrane is kept in the deionized water of 0～5 ℃ stand-by.
Comparative example 2 is prepared the reverse osmosis composite membrane of surperficial covalence graft Macrogol 2000 by m-phenylene diamine (MPD) and trimesoyl chloride
Step 1, be that molecular cut off that the aqueous solution of the m-phenylene diamine (MPD) of 2.0g/100mL evenly is poured over hygrometric state is 20000 porous polysulfone supporting layer surface with the mass body volume concentrations, cover 1 minute, topple over and remove unnecessary amine liquid, air dried 1 minute, obtained the porous polysulfone supporting layer that surface coverage has the m-phenylene diamine (MPD) aqueous solution;
Step 2, be that the IsopaG solution of the trimesoyl chloride of 0.2g/100mL evenly is poured over the porous polysulfone supporting layer surface that obtains in step 1 with the mass body volume concentrations, carried out interface polymerization reaction 20 seconds, obtain the composite membrane that surface coverage has active separating layer;
Step 3, the composite membrane that obtains in step 2 is carried out heat treatment for the first time, heating is 4 minutes under 70 ℃;
Step 4, acetone soln contacts 1 minute at 40 ℃ of lower single faces with being the Macrogol 2000 of 0.5g/100mL through the composite membrane after heat treatment for the first time and mass body volume concentrations in step 3, then be rinsing 30 minutes in the deionized water of 50 ℃ in temperature, rinse out the Macrogol 2000 of composite membrane surface physics absorption, carry out immediately heat treatment for the second time, under 80 ℃, heating is 5 minutes, obtain the hydrophily reverse osmosis composite membrane of covalence graft, this reverse osmosis composite membrane is kept in the deionized water of 0～5 ℃ stand-by.
Comparative example 3 is prepared the reverse osmosis composite membrane of surperficial covalence graft PEG400 by m-phenylene diamine (MPD) and trimesoyl chloride
Step 1, be that molecular cut off that the aqueous solution of the m-phenylene diamine (MPD) of 2.0g/100mL evenly is poured over hygrometric state is 20000 porous polysulfone supporting layer surface with the mass body volume concentrations, cover 1 minute, topple over and remove unnecessary amine liquid, air dried 1 minute, obtained the porous polysulfone supporting layer that surface coverage has the m-phenylene diamine (MPD) aqueous solution;
Step 2, be that the IsopaG solution of the trimesoyl chloride of 0.2g/100mL evenly is poured over the porous polysulfone supporting layer surface that obtains in step 1 with the mass body volume concentrations, carried out interface polymerization reaction 20 seconds, obtain the composite membrane that surface coverage has active separating layer;
Step 3, the composite membrane that obtains in step 2 is carried out heat treatment for the first time, heating is 4 minutes under 70 ℃;
Step 4, acetone soln contacts 1 minute at 40 ℃ of lower single faces with being the PEG400 of 0.5g/100mL through the composite membrane after heat treatment for the first time and mass body volume concentrations in step 3, then be rinsing 30 minutes in the deionized water of 50 ℃ in temperature, rinse out the PEG400 of composite membrane surface physics absorption, carry out immediately heat treatment for the second time, under 80 ℃, heating is 5 minutes, obtain the hydrophily reverse osmosis composite membrane of covalence graft, this reverse osmosis composite membrane is kept in the deionized water of 0～5 ℃ stand-by.
Comparative example 4 is prepared the reverse osmosis composite membrane of the PEG400 of surperficial covalence graft amido end-blocking by m-phenylene diamine (MPD) and trimesoyl chloride
Step 1, be that molecular cut off that the aqueous solution of the m-phenylene diamine (MPD) of 2.0g/100mL evenly is poured over hygrometric state is 20000 porous polysulfone supporting layer surface with the mass body volume concentrations, cover 1 minute, topple over and remove unnecessary amine liquid, air dried 1 minute, obtained the porous polysulfone supporting layer that surface coverage has the m-phenylene diamine (MPD) aqueous solution;
Step 2, be that the IsopaG solution of the trimesoyl chloride of 0.2g/100mL evenly is poured over the porous polysulfone supporting layer surface that obtains in step 1 with the mass body volume concentrations, carried out interface polymerization reaction 20 seconds, obtain the composite membrane that surface coverage has active separating layer;
Step 3, the composite membrane that obtains in step 2 is carried out heat treatment for the first time, heating is 4 minutes under 70 ℃;
Step 4, the acetone soln of PEG400 contacts 1 minute at 40 ℃ of lower single faces with being the amido end-blocking of 0.5g/100mL through the composite membrane after heat treatment for the first time and mass body volume concentrations in step 3, then be rinsing 30 minutes in the deionized water of 50 ℃ in temperature, rinse out the PEG400 of the amido end-blocking of composite membrane surface physics absorption, carry out immediately heat treatment for the second time, under 80 ℃, heating is 5 minutes, obtain the hydrophily reverse osmosis composite membrane of covalence graft, this reverse osmosis composite membrane is kept in the deionized water of 0～5 ℃ stand-by.
The concrete preparation process of embodiment 2 to embodiment 15 is with embodiment 1, the performance test results of concrete condition and step and film is referring to table one, table two and table three, the film properties test condition that adopts is: the sodium-chloride water solution of 2000ppm, operating pressure are 1.5MPa, and probe temperature is 25 ℃.
Table one
In table one, the water contact angle of the reverse osmosis composite membrane of comparative example 1 preparation is 65 °, and water flux is 47.2L/m
2H, salt rejection rate is 98.2%, and the water contact angle of the reverse osmosis composite membrane of comparative example 2 preparations is 62 °, and water flux is 48.5L/m
2H, salt rejection rate is 98.9%, the thickness of hydrophilic coating is 8nm, and the water contact angle of the reverse osmosis composite membrane of embodiment 1～5 preparation to be respectively be 53 °, 53 °, 53 °, 52 ° and 51 °, water flux is respectively 54.6L/m
2H, 54.1L/m
2H, 55.2L/m
2H, 54.5L/m
2H and 56.8L/m
2H, salt rejection rate is respectively 99.38%, 99.39%, 99.48%, 99.57% and 99.65%, the thickness of hydrophilic coating is respectively 34nm, 36nm, 37nm, 48nm and 53nm, and hence one can see that: the contact angle of reverse osmosis composite membrane of the present invention is far smaller than the contact angle by the reverse osmosis composite membrane of m-phenylene diamine (MPD) and trimesoyl chloride preparation; Hydrophily and contamination resistance that reverse osmosis composite membrane of the present invention is described are better.
The hydrophilic coating thickness of reverse osmosis composite membrane of the present invention is apparently higher than the hydrophilic coating thickness of the reverse osmosis composite membrane that is prepared by m-phenylene diamine (MPD) and trimesoyl chloride; Show thus: the end group of reverse osmosis composite membrane of the present invention surface covalence graft is that the content of hydrophilic polymer of hydroxyl is obviously more than the reverse osmosis composite membrane by m-phenylene diamine (MPD) and trimesoyl chloride preparation, show that polynary acyl chlorides is when the covalence graft hydrophilic polymer, more tie point can be provided, improve the content of surface grafting polymerization thing.The raising of surface hydrophilicity polymer content has also correspondingly improved hydrophily, contamination resistance and the salt rejection of reverse osmosis composite membrane.Therefore the water flux of reverse osmosis composite membrane of the present invention and salt rejection rate are all apparently higher than water flux and salt rejection rate by the reverse osmosis composite membrane of m-phenylene diamine (MPD) and trimesoyl chloride preparation; This shows, the combination property of reverse osmosis composite membrane of the present invention all obviously is better than the reverse osmosis composite membrane by m-phenylene diamine (MPD) and trimesoyl chloride preparation.
Table two
In table two, the water contact angle of the reverse osmosis composite membrane of comparative example 3 preparations is 62 °, and water flux is 47.5L/m
2H, salt rejection rate is 98.6%, the thickness of hydrophilic coating is 4nm, and the water contact angle of the reverse osmosis composite membrane of embodiment 6～10 preparations is respectively 52 °, 53 °, 51 °, 51 ° and 50 °, water flux is respectively 53.6L/m
2H, 55.2L/m
2H, 55.6L/m
2H, 56.2L/m
2H and 56.8L/m
2H, salt rejection rate is respectively 99.37%, 99.45%, 99.51%, 99.83% and 99.67%, the thickness of hydrophilic coating is respectively 19nm, 20nm, 20nm, 26nm and 29nm, and hence one can see that: the contact angle of reverse osmosis composite membrane of the present invention is far smaller than the contact angle by the reverse osmosis composite membrane of m-phenylene diamine (MPD) and trimesoyl chloride preparation; Hydrophily and contamination resistance that reverse osmosis composite membrane of the present invention is described are better.
The hydrophilic coating thickness of reverse osmosis composite membrane of the present invention is apparently higher than the hydrophilic coating thickness of the reverse osmosis composite membrane that is prepared by m-phenylene diamine (MPD) and trimesoyl chloride; Show thus: the end group of reverse osmosis composite membrane of the present invention surface covalence graft is that the content of hydrophilic polymer of hydroxyl is obviously more than the reverse osmosis composite membrane by m-phenylene diamine (MPD) and trimesoyl chloride preparation, show that polynary acyl chlorides is when the covalence graft hydrophilic polymer, more tie point can be provided, improve the content of surface grafting polymerization thing.The raising of surface hydrophilicity polymer content has also correspondingly improved hydrophily, contamination resistance and the salt rejection of reverse osmosis composite membrane.Therefore the water flux of reverse osmosis composite membrane of the present invention and salt rejection rate are all apparently higher than water flux and salt rejection rate by the reverse osmosis composite membrane of m-phenylene diamine (MPD) and trimesoyl chloride preparation; This shows, the combination property of reverse osmosis composite membrane of the present invention all obviously is better than the reverse osmosis composite membrane by m-phenylene diamine (MPD) and trimesoyl chloride preparation.
Table three
In table three, comparative example 4 is 63 ° for the water contact angle of the reverse osmosis composite membrane of preparation, and water flux is 46.5L/m
2H, salt rejection rate is 98.9%, the thickness of hydrophilic coating is 5nm, and the water contact angle of the reverse osmosis composite membrane of embodiment 11～15 preparations is respectively 53 °, 53 °, 52 °, 52 ° and 51 °, water flux is respectively 54.2L/m
2H, 54.8L/m
2H, 55.7L/m
2H, 56.7L/m
2H and 56.5L/m
2H, salt rejection rate is respectively 99.25%, 99.37%, 99.48%, 99.63% and 99.62%, the thickness of hydrophilic coating is respectively 20nm, 21nm, 20nm, 25nm and 30nm, and hence one can see that: the contact angle of reverse osmosis composite membrane of the present invention is far smaller than the contact angle by the reverse osmosis composite membrane of m-phenylene diamine (MPD) and trimesoyl chloride preparation; Hydrophily and contamination resistance that reverse osmosis composite membrane of the present invention is described are better.
The hydrophilic coating thickness of reverse osmosis composite membrane of the present invention is apparently higher than the hydrophilic coating thickness of the reverse osmosis composite membrane that is prepared by m-phenylene diamine (MPD) and trimesoyl chloride; Show thus: the end group of reverse osmosis composite membrane of the present invention surface covalence graft is that the content of hydrophilic polymer of amido is obviously more than the reverse osmosis composite membrane by m-phenylene diamine (MPD) and trimesoyl chloride preparation, show that polynary acyl chlorides is when the covalence graft hydrophilic polymer, more tie point can be provided, improve the content of surface grafting polymerization thing.The raising of surface hydrophilicity polymer content has also correspondingly improved hydrophily, contamination resistance and the salt rejection of reverse osmosis composite membrane.Therefore the water flux of reverse osmosis composite membrane of the present invention and salt rejection rate are all apparently higher than water flux and salt rejection rate by the reverse osmosis composite membrane of m-phenylene diamine (MPD) and trimesoyl chloride preparation; This shows, the combination property of reverse osmosis composite membrane of the present invention all obviously is better than the reverse osmosis composite membrane by m-phenylene diamine (MPD) and trimesoyl chloride preparation
Obviously, above-described embodiment is only for example clearly is described, and is not the restriction to embodiment; For the person of an ordinary skill in the technical field, can also make other changes in different forms on the basis of the above description; Here need not also can't give all embodiments exhaustive; And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (10)
1. a hydrophily reverse osmosis composite membrane, is characterized in that, this composite membrane comprises:
Molecular cut off is 20000～50000 porous polysulfone supporting layer;
Be compound in the active separating layer on described porous polysulfone supporting layer surface, the polymer of described active separating layer for being obtained by interfacial polymerization by m-phenylene diamine (MPD) and the polynary acyl chlorides of biphenyl;
Be coated on the hydrophilic coating on described active separating layer surface, described hydrophilic coating is hydrophilic polymer.
2. a kind of hydrophily reverse osmosis composite membrane according to claim 1, is characterized in that, the polynary acyl chlorides of described biphenyl is 2,2 ', 4,4 '-biphenyl four acyl chlorides, 2,2 ', 5,5 '-biphenyl four acyl chlorides, 3,3 ', 5,5 '-biphenyl four acyl chlorides, 2,3 ', 4,5 ', 6,-biphenyl five acyl chlorides or 2,2 ', 4,4 ', 6,6 '-biphenyl six acyl chlorides;
Described 2,2 ', 4,4 '-structural formula of biphenyl four acyl chlorides is:
Described 2,2 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
Described 3,3 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
Described 2,3 ', 4,5 ', 6, the structural formula of-biphenyl five acyl chlorides is:
Described 2,2 ', 4,4 ', 6,6 '-structural formula of biphenyl six acyl chlorides is:
3. a kind of hydrophily reverse osmosis composite membrane according to claim 1, is characterized in that, described hydrophilic polymer is that PEG400, Macrogol 2000, molecular weight are 400～20000 polyvinyl alcohol or the PEG400 of amido end-blocking.
4. the preparation method of a kind of hydrophily reverse osmosis composite membrane as claimed in claim 1, is characterized in that, condition and the step of the method are as follows:
Step 1, be that molecular cut off that the aqueous solution of the m-phenylene diamine (MPD) of 1.5g/100mL～3g/100mL evenly is poured over hygrometric state is 20000～50000 porous polysulfone supporting layer surface with the mass body volume concentrations, obtain the porous polysulfone supporting layer that surface coverage has m-phenylene diamine (MPD);
Step 2, be that the IsopaG of the polynary acyl chlorides of biphenyl of 0.05g/100mL～0.2g/100mL and the mixed solution of toluene evenly are poured over the porous polysulfone supporting layer surface that obtains in step 1 with the mass body volume concentrations, carry out interface polymerization reaction, obtain the composite membrane that surface coverage has active separating layer;
Step 3, the composite membrane that obtains in step 2 is heat-treated, heated 2～7 minutes under 50 ℃～90 ℃;
Step 4, the acetone soln single face that is the hydrophilic polymer of 0.01g/100mL～1g/100mL with the composite membrane after Overheating Treatment in step 3 and mass body volume concentrations contact, rinse out the hydrophilic polymer of composite membrane surface physics absorption with deionized water, obtain the hydrophily reverse osmosis composite membrane by the hydrophilic polymer covalence graft.
5. the preparation method of a kind of hydrophily reverse osmosis composite membrane according to claim 4, is characterized in that, the polynary acyl chlorides of described biphenyl is 2,2 ', 4,4 '-biphenyl four acyl chlorides, 2,2 ', 5,5 '-biphenyl four acyl chlorides, 3,3 ', 5,5 '-biphenyl four acyl chlorides, 2,3 ', 4,5 ', 6,-biphenyl five acyl chlorides or 2,2 ', 4,4 ', 6,6 '-biphenyl six acyl chlorides;
Described 2,2 ', 4,4 '-structural formula of biphenyl four acyl chlorides is:
Described 2,2 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
Described 3,3 ', 5,5 '-structural formula of biphenyl four acyl chlorides is:
Described 2,3 ', 4,5 ', 6, the structural formula of-biphenyl five acyl chlorides is:
Described 2,2 ', 4,4 ', 6,6 '-structural formula of biphenyl six acyl chlorides is:
6. the preparation method of a kind of hydrophily reverse osmosis composite membrane according to claim 4, it is characterized in that, described active separating layer is for being the polymer that the m-phenylene diamine (MPD) of 1.5g/100mL～3g/100mL and the polynary acyl chlorides of biphenyl that the mass body volume concentrations is 0.05g/100mL～0.2g/100mL obtain by interfacial polymerization by the mass body volume concentrations.
7. the preparation method of a kind of hydrophily reverse osmosis composite membrane according to claim 4, it is characterized in that, described hydrophilic polymer is that PEG400, Macrogol 2000, molecular weight are 400～20000 polyvinyl alcohol or the PEG400 of amido end-blocking.
8. the preparation method of a kind of hydrophily reverse osmosis composite membrane according to claim 4, is characterized in that, the mass body volume concentrations of described m-phenylene diamine (MPD) is 2.0g/100mL.
9. the preparation method of a kind of hydrophily reverse osmosis composite membrane according to claim 4, is characterized in that, the mass body volume concentrations of the polynary acyl chlorides of described biphenyl is 0.2g/100mL.
10. the preparation method of a kind of hydrophily reverse osmosis composite membrane according to claim 4, is characterized in that, the mass body volume concentrations of described hydrophilic polymer is 0.5g/100mL.
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| CN105153455A (en) * | 2015-08-12 | 2015-12-16 | 中国科学院长春应用化学研究所 | Biological pollution resistant material and preparation method thereof |
| CN107469649A (en) * | 2017-09-05 | 2017-12-15 | 湖南澳维环保科技有限公司 | A kind of hydrophilic anti-pollution polyamide composite reverse osmosis membrane and preparation method thereof |
| CN108043252A (en) * | 2017-12-01 | 2018-05-18 | 贵阳时代沃顿科技有限公司 | A kind of high-performance reverse osmosis composite membrane and preparation method thereof |
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| CN107469649B (en) * | 2017-09-05 | 2021-05-14 | 湖南澳维环保科技有限公司 | Hydrophilic anti-pollution polyamide composite reverse osmosis membrane and preparation method thereof |
| CN108043252A (en) * | 2017-12-01 | 2018-05-18 | 贵阳时代沃顿科技有限公司 | A kind of high-performance reverse osmosis composite membrane and preparation method thereof |
| CN108043252B (en) * | 2017-12-01 | 2020-10-30 | 时代沃顿科技有限公司 | High-performance reverse osmosis composite membrane and preparation method thereof |
| CN112867555A (en) * | 2018-10-11 | 2021-05-28 | 新加坡国立大学 | Anti-fouling polymers for reverse osmosis and membranes comprising the same |
| CN110052179A (en) * | 2019-04-18 | 2019-07-26 | 万华化学集团股份有限公司 | A kind of preparation method of antipollution composite nanometer filtering film |
| CN110052179B (en) * | 2019-04-18 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of anti-pollution composite nanofiltration membrane |
| CN111001298A (en) * | 2019-12-30 | 2020-04-14 | 天津天元新材料科技有限公司 | Preparation method of modified reverse osmosis membrane |
| CN115260494A (en) * | 2022-07-20 | 2022-11-01 | 中国科学院长春应用化学研究所 | Polyimide, thin-layer composite film thereof and preparation method |
| CN115260494B (en) * | 2022-07-20 | 2024-03-01 | 中国科学院长春应用化学研究所 | Polyimide and thin-layer composite film thereof and preparation method |
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