CN104437111A - Anti-pollution polyamide composite membrane and preparation method thereof - Google Patents
Anti-pollution polyamide composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention firstly aims at providing an anti-pollution polyamide composite membrane, comprising a nonwoven fabric layer, a polysulfone support layer, a polyamide layer and an anti-pollution layer which are sequentially arranged, wherein the anti-pollution layer comprises an antibacterial hydrophilic crosslinked polymer which is obtained by crosslinking reaction of a broad-spectrum antibacterial agent containing hydroxyalkyl, a hydrophilic polymer and a crosslinking agent. The anti-pollution polyamide composite membrane provided by the invention has a simplified overall structure, has good microbial resistance and antifouling property due to the design of the anti-pollution layer, and has relatively high water flux and salt rejection capability and long service life. The invention secondly aims at providing a preparation method of the anti-pollution polyamide composite membrane. The preparation method comprises the following steps: preparing an anti-pollution solution; preparing a base body comprising the nonwoven fabric layer, the polysulfone support layer and the polyamide layer; and forming the anti-pollution layer. The preparation method is simple in preparation process and short in production cycle; the obtained anti-pollution polyamide composite membrane has good microbial resistance and antifouling property; and relatively high water flux and salt rejection capability and long service life are kept.
Description
Technical field
The present invention relates to water-treatment technology field, especially, relate to a kind of antipollution polyamide composite film and preparation method thereof.
Background technology
Aromatic polyamides composite membrane forms one deck polyamide separating layer (such as US5160619 by interfacial polymerization in non-woven fabrics, polysulfone supporting layer, CN1261818A etc.), there is the advantages such as salt rejection rate is high, flux is large, chemical stability is excellent, the requirement of pH value range wide (4-11), operating pressure is low, become the reverse osmosis composite membrane kind be most widely used.But because aromatic polyamide membrane hydrophily is poor, film is surperficial comparatively coarse, be extremely easily subject to organic and inorganic thing and microbial contamination, membrane pollution problem is still the critical problem affecting polyamide composite film application, and seriously hinders the popularization of composite membrane.In actual applications, all can there is pollution (precipitation of calcium carbonate, metal oxide deposits, organic substance precipitation, microorganism precipitation etc.) in various degree in membrane component, system inlet outlet pressure differential is caused to increase, aquifer yield reduces, salt rejection rate declines, and then affect the normal operation of counter-infiltration system, if do not controlled as early as possible, polluting and will damage membrane component within the relatively short time.
Hydrophilic polymer is as polyvinyl alcohol (PVA), polyethylene glycol (PEG), polymine (PEI) etc. is the water-soluble high-molecular material that a class antifouling property is good, top layer hydrophilic polymer being coated on polyamide composite film enhances the antifouling property of composite membrane, and it is little to other performance impacts of composite membrane, patent CN101130444A applies PVA solution on the surface successively at aramid layer and contains the solution of crosslinking agent and catalyst, then high-temperature cross-linking forms high crosslinked PVA anti-pollution layer, improve the intensity of PVA anti-pollution layer, thus the water resistant that improve composite membrane is washed away and solubility property, improve its anti-inorganic matter and Organic Pollution ability.
Separately there is patent literature (as application publication number: CN101695636A, CN101816900A), by 3-methylol-5,5-DMH, 3-pi-allyl-5,5-DMH are grafted to aromatic polyamide membrane surface, and obtained film has chlorine-resistant and antimicrobial properties.But due to adopt the PA membrane prepared of grafting method not only have percent grafting low, affect film surface potential and hydrophily causes the shortcomings such as the decline of composite membrane separating property, complex process, but also membrane structure can be destroyed, the mechanical performance of reduction film.
Therefore, invent a kind of long service life, there is very strong antifouling effect and the simple film tool of preparation method has very important significance.
Summary of the invention
The first object of the present invention is that providing a kind of is coated on the surface of polyamide film layer by broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent being carried out the crosslinked anti-soil layer obtained, and the polyamide composite film with very strong contamination resistance (resisting microbial contamination, anti-organic pollution and anti-inorganic pollution) obtained, the long service life of composite membrane, application is wide.Concrete technical scheme is as follows:
A kind of antipollution polyamide composite film, comprises the nonwoven layer, polysulfone supporting layer, aramid layer and the anti-pollution layer that set gradually;
Described anti-pollution layer comprises the antibacterial hydrophilic crosslinked polymer being existed by the broad spectrum antimicrobicide containing hydroxyalkyl, hydrophilic polymer and crosslinking agent at water and catalyst and carry out cross-linking reaction under 50-120 DEG C of condition and obtain.
Preferred in above technical scheme, described broad spectrum antimicrobicide is at least one in triazole type, dicarboximide class, morpholine class, thiocarbamates, phenylpyrrole class, benzimidazole, pyrazoles, glycolylurea class, miazines and pyroles, be preferably 5-amino-1-hydroxyethyl pyrazoles, 4,5-diaminostilbene-(2-ethoxy) pyrazoles, 1,3-dihydroxymethyl-5,5-DMH, 1-methylol-5,5-DMH and 1, at least one in 3-dihydroxy ethyl-5,5-DMH.
Preferred in above technical scheme, be calculated in mass percent, the content of described broad spectrum antimicrobicide is 0.01-10%, is preferably 0.1-3%.
Preferred in above technical scheme, described hydrophilic polymer is at least one in polyvinyl alcohol, polyethylene glycol and polymine; Be preferably the degree of polymerization to be 200-4000 and alcoholysis degree be the polyvinyl alcohol of 75-100%, polyethylene glycol that mean molecule quantity is 200-100000 and mean molecule quantity are at least one in the polymine of 300-80000.
Preferred in above technical scheme, be calculated in mass percent, the content of described hydrophilic polymer is 0.01-5%, is preferably 0.1-2%.
In above technical scheme preferably, described crosslinking agent is any one in glyoxal, butanedial, hexandial, glutaraldehyde and boric acid; Described catalyst is any one in hydrochloric acid, nitric acid, phosphoric acid, formic acid and acetic acid, preferably adopts concentration to be the hydrochloric acid of 37%.
Preferred in above technical scheme, the thickness of described aramid layer is 50-300nm, and the thickness of described anti-pollution layer is 20-200nm.
Apply antipollution polyamide composite film of the present invention, there is following beneficial effect:
(1) antipollution polyamide composite film of the present invention comprises the nonwoven layer, polysulfone supporting layer, aramid layer and the anti-pollution layer that set gradually, anti-pollution layer comprises and under water and catalyst exist, carries out cross-linking reaction by the broad spectrum antimicrobicide containing hydroxyalkyl, hydrophilic polymer and crosslinking agent and the cross-linked polymer that obtains, and overall structure is simplified; Anti-pollution layer adopts the design of the cross-linked polymer obtained containing the broad spectrum antimicrobicide of hydroxyalkyl, hydrophilic polymer and crosslinking agent generation cross-linking reaction, microbial resistance can and antifouling property good, there is higher water flux and salt-stopping rate, long service life.
(2) in the present invention, broad spectrum antimicrobicide selects triazole type, dicarboximide class, morpholine class, thiocarbamates, phenylpyrrole class, benzimidazole, pyrazoles, glycolylurea class, at least one in miazines and pyroles, preferably 5-amino-1-hydroxyethyl pyrazoles, 4, 5-diaminostilbene-(2-ethoxy) pyrazoles, 1, 3-dihydroxymethyl-5, 5-DMH, 1-methylol-5, 5-DMH and 1, 3-dihydroxy ethyl-5, at least one in 5-DMH, can well with hydrophilic polymer generation cross-linking reaction, antifouling property is good, its consumption is calculated in mass percent as 0.01-10%, and preferably 0.1-3% is cost-saving when reaching best antibacterial effect.
(3) in the present invention, hydrophilic polymer is at least one in polyvinyl alcohol, polyethylene glycol and polymine, preferably: the degree of polymerization of polyvinyl alcohol is 200-4000, and its alcoholysis degree is 75-100%; The mean molecule quantity of polyethylene glycol is 200-100000; The mean molecule quantity of polymine is 300-80000, cost low and can well with broad spectrum antimicrobicide generation cross-linking reaction, improve further the antipollution effect of composite membrane; Its consumption is calculated in mass percent as 0.01-10%, preferably 0.1-3%, and proportioning is suitable, and cost is low.
(4) in the present invention, the thickness of aramid layer is 50-300nm, the thickness of anti-pollution layer is 20-200nm, the thickness of aramid layer is reasonable in design, anti-pollution layer can be carried well, the thickness of anti-pollution layer arranges the demand that can meet existing liquid filtering, reach good microbial resistance energy and antifouling property, there is higher water flux and salt-stopping rate, long service life.
The second object of the present invention is the preparation method providing a kind of antipollution polyamide composite film, comprises the following steps:
Step one: preparation antipollution solution, is specially: be dissolved in by the broad spectrum antimicrobicide containing hydroxyalkyl in the aqueous solution containing hydrophilic polymer; Add catalyst and crosslinking agent antipollution solution again;
Step 2: the nonwoven layer set gradually, polysulfone supporting layer and aramid layer;
Step 3: the antipollution solution prepared in described step one is coated on described aramid layer and cross-linking reaction formation anti-pollution layer occurs under 50-120 DEG C of condition, obtain antipollution polyamide composite film.
Preferred in above technical scheme, the setting up procedure of described polysulfone supporting layer and aramid layer is specially: first polysulfone supporting layer contacted with the many ammonia solutions containing at least two reactive amino compounds, remove unnecessary solution by rubber rollers, form many ammonia solutions layer on the surface in polysulfone supporting layer; Again the polysulfone supporting layer obtained is contacted with the solution of acid chloride at least containing two reactive acid chloride groups and form aramid layer.
Preferred in above technical scheme, under temperature is 60-100 DEG C of condition, cross-linking reaction occurs in described step 3, preferable temperature is 80 DEG C;
The thickness of described aramid layer is 50-300nm, and the thickness of described anti-pollution layer is 20-200nm;
Described hydrophilic polymer is preferably at least one in polyvinyl alcohol, polyethylene glycol and polymine, is preferably the degree of polymerization to be 200-4000 and alcoholysis degree be the polyvinyl alcohol of 75-100%, polyethylene glycol that mean molecule quantity is 200-100000 and mean molecule quantity are at least one in the polymine of 300-80000;
Described broad spectrum antimicrobicide is at least one in triazole type, dicarboximide class, morpholine class, thiocarbamates, phenylpyrrole class, benzimidazole, pyrazoles, glycolylurea class, miazines and pyroles, be preferably 5-amino-1-hydroxyethyl pyrazoles, 4,5-diaminostilbene-(2-ethoxy) pyrazoles, 1,3-dihydroxymethyl-5,5-DMH, 1-methylol-5, at least one in 5-DMH and 1,3-dihydroxy ethyl-5,5-DMH;
Be calculated in mass percent, the content of described hydrophilic polymer is 0.01-5%, is preferably 0.1-2%;
Be calculated in mass percent, the content of described broad spectrum antimicrobicide is 0.01-10%, is preferably 0.1-3%;
Described crosslinking agent is any one in glyoxal, butanedial, hexandial, glutaraldehyde and boric acid;
Described catalyst is any one in hydrochloric acid, nitric acid, phosphoric acid, formic acid and acetic acid, preferably adopts concentration to be the hydrochloric acid of 37%.
Apply preparation method of the present invention, there is following technique effect: preparation process is simple, with short production cycle; Microbial resistance energy and the antifouling property of gained antipollution polyamide composite film are good, keep higher water flux and salt-stopping rate, long service life.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the Electronic Speculum figure of the antipollution polyamide composite film of the preferred embodiment of the present invention 1;
Fig. 2 is the Electronic Speculum figure of traditional polyamide composite film of comparative example;
Fig. 3 is that comparative example and embodiment 1-embodiment 9 use the decay of water flux in Contamination measurement liquid test process to the percent value of film initial water flux.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail, but the multitude of different ways that the present invention can limit according to claim and cover is implemented.
Embodiment 1:
A kind of antipollution polyamide composite film, comprise the nonwoven layer, polysulfone supporting layer, aramid layer and the anti-pollution layer that set gradually, described anti-pollution layer comprises and under water and catalyst existence condition, carries out cross-linking reaction by the broad spectrum antimicrobicide containing hydroxyalkyl, hydrophilic polymer and crosslinking agent and the cross-linked polymer that obtains, wherein cross-linking reaction refer to 2 or more molecule (being generally linear molecule) mutually bonding cross-linking become the comparatively stable molecule (build molecule) of network structure to react; The thickness of described aramid layer is 50-300nm, and the thickness of described anti-pollution layer is 20-200nm.
The described broad spectrum antimicrobicide containing hydroxyalkyl selects 5-amino-1-hydroxyethyl pyrazoles, its content for 0.1% (content of broad spectrum antimicrobicide refers to herein: the quality of broad spectrum antimicrobicide account for prepare antipollution solution adopt the weight sum of raw material); Described hydrophilic polymer selects that the degree of polymerization is 1400, alcoholysis degree is the polyvinyl alcohol of 99%, its content for 0.3% (content of hydrophilic polymer refers to herein: the quality of hydrophilic polymer account for prepare antipollution solution adopt the weight sum of raw material); Described crosslinking agent is glutaraldehyde; Catalyst adopts concentration to be the hydrochloric acid of 50%.
Prepare antipollution polyamide composite film according to the following steps:
The first step: preparation antipollution solution, is specially: (1) first takes 3 grams of polyvinyl alcohol and adds in 966 grams of deionized waters and be heated to 95 DEG C, is stirred to and dissolves completely; Add 10 grams of glutaraldehydes after being cooled to normal temperature and 20 grams of concentration are the hydrochloric acid of 37%, stir, (2) take 1 gram of 5-amino-1-hydroxyethyl pyrazoles again and join in the solution of (1) gained to be stirred to and mix;
Second step: the nonwoven layer set gradually, polysulfone supporting layer and aramid layer, the preparation process of wherein said polysulfone supporting layer is specially: take polysulfone resin (PSF) 80 grams, N, dinethylformamide (DMF) 370 grams and Macrogol 200 (PEG200) 50 grams, be hybridly prepared into the solution of 500 grams; At 75 DEG C, stir 6h, be mixed with homodisperse casting solution; Casting solution after filtration, after vacuum outgas, knifing machine is spread evenly across on non-woven fabrics, wet-film thickness is 180 μm, after at room temperature evaporating 3s, immerse gel solidification film forming in the ultra-pure water of 10 DEG C, after diaphragm is solidified completely through normal-temperature water, finally film is processed 3min in 75 DEG C of water, obtain polysulfones support basic unit;
The setting up procedure of described aramid layer is specially: take m-phenylene diamine (MPD) 240 grams, triethylamine 88 grams, camphorsulfonic acid 184 grams and dodecyl sodium sulfate 8 grams and be dissolved in 7480 grams of deionized waters, stir and obtain polyamines aqueous phase solution; 8 grams of pyromellitic trimethylsilyl chlorides are dissolved in 7992 grams of n-hexanes, stir and obtain acyl chlorides oil-phase solution; First polysulfone supporting layer is contacted 25s with polyamines aqueous phase solution, remove unnecessary solution by rubber rollers, form many ammonia solutions layer on the surface in polysulfone supporting layer; Again the polysulfone supporting layer obtained is contacted 20s with acyl chlorides oil-phase solution, remove the remaining oil-phase solution on surface, form aramid layer, obtain the first matrix;
3rd step: the antipollution solution prepared in described step one is coated on the aramid layer in described first matrix and keeps 10 seconds, remove unnecessary antipollution solution, the baking oven finally the first matrix being coated with antipollution solution being put into 80 DEG C is incubated 10 minutes, obtains antipollution polyamide composite film.
In above-mentioned steps, the tandem of the first step and second step can be exchanged according to the actual requirements.
The structural formula that the cross-linked polymer of crosslinked gained occurs for above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent is as follows:
Wherein m+n=1, m>0, n>0.
The surperficial Electronic Speculum figure of above-mentioned polyamide composite film refers to Fig. 1.
Above-mentioned polyamide composite film is tested, be specially: get diaphragm and test on cross-current type diaphragm monitor station, the 2000ppmNaCl aqueous solution, operating pressure be 225psi, temperature tests under be 25 DEG C and pH value being the test condition of about 7.0, acquired results is in table 1.
The Electronic Speculum figure (Fig. 1) of antipollution polyamide composite film (embodiment 1) obtained as can be seen from technical solution of the present invention and the contrast of the Electronic Speculum figure (Fig. 2) of traditional polyamide composite film (comparative example), the surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 1) is traditional is thicker more smooth, therefore, antipollution polyamide composite film more scratch resistant and the anti-pollution that obtain of technical solution of the present invention.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 1) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Embodiment 2:
A kind of antipollution polyamide composite film, difference from Example 1 is:
The described broad spectrum antimicrobicide containing hydroxyalkyl selects 4,5-diaminostilbene-(2-ethoxy) pyrazoles.
Above-mentioned polyamide composite film is carried out test acquired results in table 1.
The structural formula that the cross-linked polymer of crosslinked gained occurs for above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent is as follows:
Wherein m+n=1, m>0, n>0.
The surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 2) is traditional is thicker more smooth, more scratch resistant and anti-pollution.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 2) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Embodiment 3:
A kind of antipollution polyamide composite film, difference from Example 1 is: the described broad spectrum antimicrobicide containing hydroxyalkyl selects 1,3-dihydroxymethyl-5,5-DMH.
Above-mentioned polyamide composite film is carried out test acquired results in table 1.The structural formula that the cross-linked polymer of crosslinked gained occurs for above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent is as follows:
Wherein m+n=1, m>0, n>0.
The surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 3) is traditional is thicker more smooth, more scratch resistant and anti-pollution.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 3) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Embodiment 4:
A kind of antipollution polyamide composite film, difference from Example 1 is:
The described broad spectrum antimicrobicide containing hydroxyalkyl selects 1-methylol-5,5-DMH.
Above-mentioned polyamide composite film is carried out test acquired results in table 1.
The structural formula that the cross-linked polymer of crosslinked gained occurs for above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent is as follows:
Wherein m+n=1, m>0, n>0.
The surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 4) is traditional is thicker more smooth, more scratch resistant and anti-pollution.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 4) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Embodiment 5:
A kind of antipollution polyamide composite film, difference from Example 1 is:
The described broad spectrum antimicrobicide containing hydroxyalkyl selects 1,3-dihydroxy ethyl-5,5-DMH.
Above-mentioned polyamide composite film is carried out test acquired results in table 1.
The structural formula that the cross-linked polymer of crosslinked gained occurs for above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent is as follows.
The surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 5) is traditional is thicker more smooth, more scratch resistant and anti-pollution.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 5) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Wherein m+n=1, m>0, n>0.
Embodiment 6:
A kind of antipollution polyamide composite film, difference from Example 1 is:
The described broad spectrum antimicrobicide containing hydroxyalkyl selects 5-amino-1-hydroxyethyl pyrazoles and 1,3-dihydroxymethyl-5,5-DMH, its consumption is respectively: take 5-amino-1 hydroxyethyl pyrazole 0.5 gram, take 1,3-dihydroxymethyl-5,5-DMH 0.5 gram.
Above-mentioned polyamide composite film is carried out test acquired results in table 1.
The structural formula that the cross-linked polymer of crosslinked gained occurs for above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent is as follows:
Wherein m+n=1, m>0, n>0.
The surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 6) is traditional is thicker more smooth, more scratch resistant and anti-pollution.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 6) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Embodiment 7:
A kind of antipollution polyamide composite film, difference from Example 1 is:
The described broad spectrum antimicrobicide containing hydroxyalkyl selects 5-amino-1-hydroxyethyl pyrazoles, 4,5-diaminostilbene-(2-ethoxy) pyrazoles, 1,3-dihydroxymethyl-5,5-DMH, 1-methylol-5,5-DMH and 1,3-dihydroxy ethyl-5,5-DMH, its consumption is respectively: take 5-amino-1 hydroxyethyl pyrazole, 4,5-diaminostilbenes-(2-ethoxy) pyrazoles, 1,3-dihydroxymethyl-5 respectively, 5-DMH, 1-methylol-5,5-DMH and each 0.2 gram of 1,3-dihydroxy ethyl-5,5-DMH.
Above-mentioned polyamide composite film is carried out test acquired results in table 1.
The structural formula that the cross-linked polymer of crosslinked gained occurs for above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent is as follows:
Wherein m+n=1, m>0, n>0.
The surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 7) is traditional is thicker more smooth, more scratch resistant and anti-pollution.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 7) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Embodiment 8:
A kind of antipollution polyamide composite film, difference from Example 1 is:
The described broad spectrum antimicrobicide containing hydroxyalkyl selects 1,3-dihydroxymethyl-5,5-DMH, its consumption respectively: take 1,3-dihydroxymethyl-5,5-DMH 1.0 grams; Described hydrophilic polymer selects polyvinyl alcohol, polyethylene glycol and polymine, and the degree of polymerization of wherein said polyvinyl alcohol is 1400, and its alcoholysis degree is 99%; The molecular weight of described polyethylene glycol is 20000; The molecular weight of described polymine is 10000; Its consumption is: each 1.0 grams of weighing polyvinyl alcohol, polyethylene glycol and polymine.
Above-mentioned polyamide composite film is carried out test acquired results in table 1.
Above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent to exist and that the structural formula of the cross-linked polymer of crosslinked gained occurs at the temperature of 80 DEG C is as follows at deionized water and catalyst:
Wherein m+n+o=1, m>0, n>0, o>0.
The surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 8) is traditional is thicker more smooth, more scratch resistant and anti-pollution.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 8) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Embodiment 9:
A kind of antipollution polyamide composite film, difference from Example 1 is:
The described broad spectrum antimicrobicide containing hydroxyalkyl selects 1,3-dihydroxymethyl-5,5-DMH and 1,3-dihydroxy ethyl-5,5-DMH, its consumption respectively: take 1,3-dihydroxymethyl-5,5-DMH and each 1.0 grams of 1,3-dihydroxy ethyl-5,5-DMH; Described hydrophilic polymer selects polyvinyl alcohol, polyethylene glycol and polymine, and the degree of polymerization of wherein said polyvinyl alcohol is 1400, and its alcoholysis degree is 99%; The molecular weight of described polyethylene glycol is 20000; The molecular weight of described polymine is 10000; Its consumption is: each 1.0 grams of weighing polyvinyl alcohol, polyethylene glycol and polymine.
Above-mentioned polyamide composite film is carried out test acquired results in table 1.
Above-mentioned broad spectrum antimicrobicide, hydrophilic polymer and crosslinking agent to exist and that the structural formula of the cross-linked polymer of crosslinked gained occurs at the temperature of 80 DEG C is as follows at deionized water and catalyst:
Wherein m+n+o=1, m>0, n>0, o>0.
The surface of the polyamide composite film (comparative example) that the surface ratio of antipollution polyamide composite film of the present invention (embodiment 9) is traditional is thicker more smooth, more scratch resistant and anti-pollution.
Tradition polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 9) percent value of decay to film initial water flux of water flux in Contamination measurement liquid test process refer to Fig. 3.
Comparative example:
The step preparing polyamide composite film in prior art is as follows:
The first step: the preparation of polyamines aqueous phase solution, is specially: take m-phenylene diamine (MPD) 240 grams, triethylamine 88 grams, camphorsulfonic acid 184 grams and dodecyl sodium sulfate 8 grams and be dissolved in 7480 grams of water, stir and obtain polyamines aqueous phase solution;
Second step: the preparation of oil-phase solution, is specially: 8 grams of pyromellitic trimethylsilyl chlorides are dissolved in 7992 grams of n-hexanes, stir and obtain acyl chlorides oil-phase solution;
3rd step: the preparation of polyamide composite film, be specially: the support membrane prepared to be immersed in the polyamines aqueous phase solution of first step gained 25 seconds, the aqueous phase solution on support membrane surface is remained in rubber rollers removing, again this film to be immersed in the acyl chlorides oil-phase solution of second step gained 20 seconds, remove the remaining oil-phase solution on surface, then to put it in 80 DEG C of baking ovens dry 5 minutes, obtain polyamide composite film.
The surperficial Electronic Speculum figure of above-mentioned polyamide composite film refers to Fig. 2.
Above-mentioned polyamide composite film is tested, be specially: get diaphragm and test on cross-current type diaphragm monitor station, in the 2000ppmNaCl aqueous solution, operating pressure is 225psi, temperature is 25 DEG C, pH value is test under the test condition of about 7.0, and acquired results is in table 1.
The test result of the polyamide composite film that table 1 embodiment 1-9 and comparative example obtain compares
From table 1, the initial salt-stopping rate of the antipollution polyamide composite film (embodiment 1-embodiment 9) that technical scheme of the present invention obtains is apparently higher than traditional polyamide composite film (comparative example), initial water flux is then lower slightly, run 12 hours in contaminated liquid after, both salt rejection rates and water flux decline all to some extent, and wherein traditional polyamide composite film (comparative example) water flux fall is greater than antipollution polyamide composite film of the present invention (embodiment 1-embodiment 9); And from the situation of reduction in colony, antipollution polyamide composite film of the present invention (embodiment 1-embodiment 9) its antimicrobial properties compared with traditional polyamide composite film (comparative example) is greatly improved (do Escherichia coli culture experiment with conventional reverse osmosis film and complex reverse osmosis membrane of the present invention and compare acquired results).
The anti-pollution ability that decay conversion in time in order to water flux carrys out evaluated for film is the common method that membrane for water treatment anti-fouling performance is evaluated.Fig. 3 is that traditional polyamide composite film (comparative example) and gained polyamide composite film of the present invention (embodiment 1-embodiment 9) use the decay of water flux in Contamination measurement liquid test process to the percent value of film initial water flux.As can be seen from Figure 3, the flux decline of gained polyamide composite film of the present invention (embodiment 1-embodiment 9) is slower than traditional polyamide composite film (comparative example), and after pure water cleaning, water flux recovers fast.This illustrates that gained polyamide composite film of the present invention (embodiment 1-embodiment 9) has better anti-fouling performance than traditional polyamide composite film (comparative example), thus, gained polyamide composite film of the present invention (embodiment 1-embodiment 9) has good anti-fouling performance, especially microbial contamination resistance performance.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an antipollution polyamide composite film, is characterized in that: comprise the nonwoven layer, polysulfone supporting layer, aramid layer and the anti-pollution layer that set gradually;
Described anti-pollution layer comprises the antibacterial hydrophilic crosslinked polymer being existed by the broad spectrum antimicrobicide containing hydroxyalkyl, hydrophilic polymer and crosslinking agent at water and catalyst and carry out cross-linking reaction under 50-120 DEG C of condition and obtain.
2. antipollution polyamide composite film according to claim 1, it is characterized in that: described broad spectrum antimicrobicide is at least one in triazole type, dicarboximide class, morpholine class, thiocarbamates, phenylpyrrole class, benzimidazole, pyrazoles, glycolylurea class, miazines and pyroles, be preferably 5-amino-1-hydroxyethyl pyrazoles, 4,5-diaminostilbene-(2-ethoxy) pyrazoles, 1,3-dihydroxymethyl-5,5-DMH, 1-methylol-5,5-DMH and 1, at least one in 3-dihydroxy ethyl-5,5-DMH.
3. antipollution polyamide composite film according to claim 2, is characterized in that: be calculated in mass percent, and the content of described broad spectrum antimicrobicide is 0.01-10%, is preferably 0.1-3%.
4. antipollution polyamide composite film according to claim 1, is characterized in that: described hydrophilic polymer is at least one in polyvinyl alcohol, polyethylene glycol and polymine; Be preferably the degree of polymerization to be 200-4000 and alcoholysis degree be the polyvinyl alcohol of 75-100%, polyethylene glycol that mean molecule quantity is 200-100000 and mean molecule quantity are at least one in the polymine of 300-80000.
5. the antipollution polyamide composite film according to claim 1-4 any one, is characterized in that: be calculated in mass percent, and the content of described hydrophilic polymer is 0.01-5%; Be preferably 0.1-2%.
6. antipollution polyamide composite film according to claim 5, is characterized in that: described crosslinking agent is any one in glyoxal, butanedial, hexandial, glutaraldehyde and boric acid; Described catalyst is any one in hydrochloric acid, nitric acid, phosphoric acid, formic acid and acetic acid, preferably adopts concentration to be the hydrochloric acid of 37%.
7. antipollution polyamide composite film according to claim 6, is characterized in that: the thickness of described aramid layer is 50-300nm, and the thickness of described anti-pollution layer is 20-200nm.
8. a preparation method for antipollution polyamide composite film, is characterized in that: comprise the following steps:
Step one: preparation antipollution solution, is specially: be dissolved in by the broad spectrum antimicrobicide containing hydroxyalkyl in the aqueous solution containing hydrophilic polymer; Add catalyst again and crosslinking agent obtains antipollution solution;
Step 2: set gradually nonwoven layer, polysulfone supporting layer and aramid layer;
Step 3: the antipollution solution prepared in described step one is coated on described aramid layer and cross-linking reaction formation anti-pollution layer occurs under 50-120 DEG C of condition, obtain antipollution polyamide composite film.
9. the preparation method of antipollution polyamide composite film according to claim 8, it is characterized in that: the setting up procedure of described polysulfone supporting layer and aramid layer is specially: first polysulfone supporting layer is contacted with the many ammonia solutions containing at least two reactive amino compounds, remove unnecessary solution by rubber rollers, form many ammonia solutions layer on the surface in polysulfone supporting layer; Again the polysulfone supporting layer obtained is contacted with the solution of acid chloride at least containing two reactive acid chloride groups and form aramid layer.
10. the preparation method of antipollution polyamide composite film according to claim 8, is characterized in that:
Under temperature is 60-100 DEG C of condition, cross-linking reaction occurs in described step 3, preferable temperature is 80 DEG C;
The thickness of described aramid layer is 50-300nm, and the thickness of described anti-pollution layer is 20-200nm;
Described hydrophilic polymer is preferably at least one in polyvinyl alcohol, polyethylene glycol and polymine, is preferably: the polyvinyl alcohol of the degree of polymerization to be 200-4000 and alcoholysis degree be 75-100%, the mean molecule quantity at least one that to be the polyethylene glycol of 200-100000 and mean molecule quantity be in the polymine of 300-80000;
Described broad spectrum antimicrobicide is at least one in triazole type, dicarboximide class, morpholine class, thiocarbamates, phenylpyrrole class, benzimidazole, pyrazoles, glycolylurea class, miazines and pyroles, be preferably 5-amino-1-hydroxyethyl pyrazoles, 4,5-diaminostilbene-(2-ethoxy) pyrazoles, 1,3-dihydroxymethyl-5,5-DMH, 1-methylol-5, at least one in 5-DMH and 1,3-dihydroxy ethyl-5,5-DMH;
Be calculated in mass percent, the content of described hydrophilic polymer is 0.01-5%, is preferably 0.1-2%;
Be calculated in mass percent, the content of described broad spectrum antimicrobicide is 0.01-10%, is preferably 0.1-3%;
Described crosslinking agent is any one in glyoxal, butanedial, hexandial, glutaraldehyde and boric acid;
Described catalyst is any one in hydrochloric acid, nitric acid, phosphoric acid, formic acid and acetic acid, preferably adopts concentration to be the hydrochloric acid of 37%.
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