CN104437111B - A kind of antipollution polyamide composite film and preparation method thereof - Google Patents
A kind of antipollution polyamide composite film and preparation method thereof Download PDFInfo
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- CN104437111B CN104437111B CN201410781491.8A CN201410781491A CN104437111B CN 104437111 B CN104437111 B CN 104437111B CN 201410781491 A CN201410781491 A CN 201410781491A CN 104437111 B CN104437111 B CN 104437111B
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Abstract
The first object of the present invention is to provide a kind of antipollution polyamide composite film, including nonwoven layer, polysulfone supporting layer, aramid layer and the anti-pollution layer set gradually；Anti-pollution layer includes the antibacterial hydrophilic crosslinked polymer as obtained from reacting the broad spectrum antimicrobial agent containing hydroxyalkyl, hydrophilic polymer and cross-linking agents.The antipollution polyamide composite film overall structure of the present invention is simplified；The design of anti-pollution layer, microbial resistance can be good with antifouling property, and with higher water flux and salt-stopping rate, service life is long.The second object of the present invention is to provide a kind of preparation method of antipollution polyamide composite film, including prepares antipollution solution；Making includes the matrix of nonwoven layer, polysulfone supporting layer and aramid layer；Form anti-pollution layer.Preparation process of the present invention is simple, with short production cycle；The microbial resistance energy and antifouling property of gained antipollution polyamide composite film are good, keep higher water flux and salt-stopping rate, and service life is long.
Description
Technical field
The present invention relates to water-treatment technology field, especially, it is related to a kind of antipollution polyamide composite film and its preparation side
Method.
Background technology
Aromatic polyamides composite membrane is to form a strata acid amides by interfacial polymerization in non-woven fabrics, polysulfone supporting layer to separate
Layer (such as US5160619, CN1261818A etc.), with salt rejection rate is high, flux is big, chemical stability is excellent, pH value range is wide
(4-11), operating pressure require low advantage, it has also become the reverse osmosis composite membrane kind being most widely used.But it is due to fragrance
PA membrane hydrophily is poor, film surface is more coarse, extremely easily by organic and inorganic thing and microorganism pollution, fouling membrane
Problem is still the critical problem of influence polyamide composite film application, and seriously hinders the popularization of composite membrane.Actually should
In, different degrees of pollution (precipitation of calcium carbonate, metal oxide deposits, organic substance precipitation, micro- life can all occur for membrane component
Thing precipitation etc.), cause system inlet outlet pressure differential to increase, aquifer yield is reduced, salt rejection rate declines, and then influence counter-infiltration system just
Often operation, if do not controlled as early as possible, pollution will damage membrane component within the relatively short time.
Hydrophilic polymer such as polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethyleneimine (PEI) etc. are a class anti-soils
Water-soluble high-molecular material of good performance is contaminated, the top layer that hydrophilic polymer is coated on into polyamide composite film enhances compound
The antifouling property of film, and other performance impacts to composite membrane are little, patent CN101130444A is on aramid layer surface
PVA solution and the solution containing crosslinking agent and catalyst are coated successively, and then high-temperature cross-linking forms the PVA antipollutions of high crosslinking
Layer, improves the intensity of PVA anti-pollution layers, so that the water resistant for improving composite membrane is washed away and solubility property, improves its anti-nothing
Machine thing and Organic Pollution ability.
Separately there is patent literature (such as application publication number：CN101695636A, CN101816900A), by 3- methylols-
5,5- DMHs, 3- pi-allyl -5,5- DMHs are grafted to aromatic polyamide membrane surface, and obtained film has resistance to
Chlorine and antimicrobial properties.But it is due to that the PA membrane prepared using grafting method not only has that grafting rate is low, influence film surface
The shortcomings of current potential and hydrophily cause compound membrane separating property decline, complex process, but also membrane structure can be destroyed, reduction film
Mechanical performance.
Therefore, invent a kind of service life length, have with very strong antifouling effect and the simple film of preparation method it is very heavy
The meaning wanted.
The content of the invention
The first object of the present invention is to provide one kind by the way that broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent are entered
The anti-soil layer that row crosslinking is obtained is coated on the surface of polyamide film layer, and obtain there is very strong contamination resistance (to resist micro- life
Thing pollution, anti-organic pollution and the pollution of anti-inorganic matter) polyamide composite film, the service life of composite membrane is long, using neck
Domain is wide.Concrete technical scheme is as follows：
A kind of antipollution polyamide composite film, including set gradually nonwoven layer, polysulfone supporting layer, aramid layer and
Anti-pollution layer；
The anti-pollution layer include by the broad spectrum antimicrobial agent containing hydroxyalkyl, hydrophilic polymer and crosslinking agent in water and
Catalyst exist and 50-120 DEG C under the conditions of carry out cross-linking reaction obtained from antibacterial hydrophilic crosslinked polymer.
Preferred in above technical scheme, the broad spectrum antimicrobial agent is triazole type, dicarboximide class, morpholine class, thio
At least one in carbamates, phenylpyrrole class, benzimidazole, pyrazoles, glycolylurea class, miazines and pyroles
Plant, preferably 5- amino-1-hydroxyethyls pyrazoles, 4,5- diaminostilbenes-(2- ethoxys) pyrazoles, 1,3- dihydroxymethyls -5,5- bis-
At least one of methyl hydantoin, 1- methylol -5,5- DMHs and 1,3- dihydroxy ethyl -5,5- DMHs.
It is preferred in above technical scheme, it is calculated in mass percent, the content of the broad spectrum antimicrobial agent is 0.01-10%,
Preferably 0.1-3%.
Preferred in above technical scheme, the hydrophilic polymer is polyvinyl alcohol, polyethylene glycol and polyethyleneimine
At least one of amine；Preferably the degree of polymerization is 200-4000 and alcoholysis degree is 75-100% polyvinyl alcohol, mean molecule
The polyethylene glycol and mean molecule quantity that amount is 200-100000 are at least one of 300-80000 polyethyleneimine.
It is preferred in above technical scheme, it is calculated in mass percent, the content of the hydrophilic polymer is 0.01-5%,
Preferably 0.1-2%.
Preferred in above technical scheme, the crosslinking agent is glyoxal, butanedial, hexandial, glutaraldehyde and boric acid
In any one；The catalyst is any one in hydrochloric acid, nitric acid, phosphoric acid, formic acid and acetic acid, it is preferred to use concentration
For 37% hydrochloric acid.
Preferred in above technical scheme, the thickness of the aramid layer is 50-300nm, the thickness of the anti-pollution layer
For 20-200nm.
Using the antipollution polyamide composite film of the present invention, have the advantages that：
(1) antipollution polyamide composite film of the invention includes the nonwoven layer, polysulfone supporting layer, polyamide set gradually
Layer and anti-pollution layer, anti-pollution layer is included to be existed by the broad spectrum antimicrobial agent containing hydroxyalkyl, hydrophilic polymer and crosslinking agent
Cross-linked polymer obtained from cross-linking reaction is carried out in the presence of water and catalyst, overall structure is simplified；Anti-pollution layer, which is used, to be contained
Broad spectrum antimicrobial agent, hydrophilic polymer and the crosslinking agent of hydroxyalkyl crosslink the design for the cross-linked polymer that reaction is obtained,
Microbial resistance can be good with antifouling property, and with higher water flux and salt-stopping rate, service life is long.
(2) present invention in broad spectrum antimicrobial agent from triazole type, dicarboximide class, morpholine class, thiocarbamates,
At least one of phenylpyrrole class, benzimidazole, pyrazoles, glycolylurea class, miazines and pyroles, preferably 5- ammonia
Base -1- hydroxyethyl pyrazoles, 4,5- diaminostilbenes-(2- ethoxys) pyrazoles, 1,3- dihydroxymethyl -5,5- DMHs, 1- hydroxyls
At least one of methyl -5,5- DMH and 1,3- dihydroxy ethyl -5,5- DMH, can well with it is hydrophilic
Property polymer crosslinks reaction, and antifouling property is good；Its consumption is calculated in mass percent as 0.01-10%, preferably 0.1-
3%, it is cost-effective in the case where reaching best antibacterial effect.
(3) hydrophilic polymer is at least one of polyvinyl alcohol, polyethylene glycol and polyethyleneimine in the present invention,
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 polyethyleneimine is 300-80000, and cost is low and can occur well with broad spectrum antimicrobial agent
Cross-linking reaction, further improves the antipollution effect of composite membrane；Its consumption is calculated in mass percent as 0.01-10%, preferably
0.1-3%, proportioning is appropriate, and cost is low.
(4) thickness of aramid layer is 50-300nm in the present invention, and the thickness of anti-pollution layer is 20-200nm, aramid layer
Thickness it is reasonable in design, anti-pollution layer can be carried well, the thickness of anti-pollution layer, which is set, can meet the need of existing liquid filtering
Ask, reach good microbial resistance energy and antifouling property, with higher water flux and salt-stopping rate, service life is long.
The second object of the present invention is to provide a kind of preparation method of antipollution polyamide composite film, including following step
Suddenly：
Step one：Antipollution solution is prepared, is specially：Broad spectrum antimicrobial agent containing hydroxyalkyl is dissolved in and gathered containing hydrophily
In the aqueous solution of compound；Add catalyst and crosslinking agent antipollution solution；
Step 2：Nonwoven layer, polysulfone supporting layer and the aramid layer set gradually；
Step 3：The antipollution solution prepared in the step one is coated on the aramid layer at 50-120 DEG C
Under the conditions of crosslink reaction and form anti-pollution layer, produce antipollution polyamide composite film.
Preferred in above technical scheme, the setting up procedure of the polysulfone supporting layer and aramid layer is specially：First will
Polysulfone supporting layer is contacted with many ammonia solutions containing at least two reactive amino compounds, is removed with rubber rollers unnecessary molten
Liquid, forms many ammonia solution layers on polysulfone supporting layer surface；Again by obtained polysulfone supporting layer with least containing two reactivity
The solution of acid chloride of acid chloride groups contacts to form aramid layer.
It is preferred in above technical scheme, in temperature it is to crosslink reaction under the conditions of 60-100 DEG C in the step 3,
Preferable temperature is 80 DEG C；
The thickness of the aramid layer is 50-300nm, and the thickness of the anti-pollution layer is 20-200nm；
The hydrophilic polymer is preferably at least one of polyvinyl alcohol, polyethylene glycol and polyethyleneimine, excellent
It is the poly- of 200-100000 to elect the polyvinyl alcohol, mean molecule quantity that the degree of polymerization is 200-4000 and alcoholysis degree is 75-100% as
Ethylene glycol and mean molecule quantity are at least one of 300-80000 polyethyleneimine；
The broad spectrum antimicrobial agent is triazole type, dicarboximide class, morpholine class, thiocarbamates, phenylpyrrole
At least one of class, benzimidazole, pyrazoles, glycolylurea class, miazines and pyroles, preferably 5- amino -1- hydroxyl second
Base pyrazoles, 4,5- diaminostilbenes-(2- ethoxys) pyrazoles, 1,3- dihydroxymethyl -5,5- DMHs, 1- methylols -5,5-
At least one of DMH and 1,3- dihydroxy ethyl -5,5- DMHs；
It is calculated in mass percent, the content of the hydrophilic polymer is 0.01-5%, preferably 0.1-2%；
It is calculated in mass percent, the content of the broad spectrum antimicrobial agent is 0.01-10%, preferably 0.1-3%；
The crosslinking agent is any one in glyoxal, butanedial, hexandial, glutaraldehyde and boric acid；
The catalyst is any one in hydrochloric acid, nitric acid, phosphoric acid, formic acid and acetic acid, it is preferred to use concentration is
37% hydrochloric acid.
Using the preparation method of the present invention, with following technique effect：Preparation process is simple, with short production cycle；Gained resists
The microbial resistance energy and antifouling property for polluting polyamide composite film are good, keep higher water flux and salt-stopping rate, use
Long lifespan.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The accompanying drawing for constituting the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its illustrate to be used to explain the present invention, do not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the electron microscope of the antipollution polyamide composite film of the preferred embodiment of the present invention 1；
Fig. 2 is the electron microscope of traditional polyamide composite film of comparative example；
Fig. 3 is comparative example and decay pair of the embodiment 1- embodiments 9 with water flux in Contamination measurement liquid test process
The percent value of the initial water flux of film.
Embodiment
Embodiments of the invention are described in detail below in conjunction with accompanying drawing, but the present invention can be limited according to claim
Fixed and covering multitude of different ways is implemented.
Embodiment 1：
A kind of antipollution polyamide composite film, including set gradually nonwoven layer, polysulfone supporting layer, aramid layer and
Anti-pollution layer, the anti-pollution layer is included by the broad spectrum antimicrobial agent containing hydroxyalkyl, hydrophilic polymer and crosslinking agent in water
With cross-linked polymer obtained from progress cross-linking reaction under catalyst existence condition, wherein cross-linking reaction refers to 2 or more
Molecule (generally linear molecule) is mutually bonded relatively stable molecule (build molecule) reaction for being cross-linked into network structure；The polyamides
The thickness of amine layer is 50-300nm, and the thickness of the anti-pollution layer is 20-200nm.
The broad spectrum antimicrobial agent containing hydroxyalkyl selects 5- amino-1-hydroxyethyl pyrazoles, and its content is 0.1% (herein
The content of broad spectrum antimicrobial agent refers to：The quality of broad spectrum antimicrobial agent, which is accounted for, prepares the weight sum that antipollution solution uses raw material)；Institute
Stating hydrophilic polymer selects the degree of polymerization to be the polyvinyl alcohol that 1400, alcoholysis degree is 99%, and its content is 0.3% (hydrophilic herein
The content of property polymer refers to：The quality of hydrophilic polymer, which is accounted for, prepares the weight sum that antipollution solution uses raw material)；Institute
Crosslinking agent is stated for glutaraldehyde；Catalyst use concentration for 50% hydrochloric acid.
Antipollution polyamide composite film is prepared according to the following steps：
The first step：Antipollution solution is prepared, is specially：(1) 3 grams of polyvinyl alcohol are first weighed to add in 966 grams of deionized waters
It is heated to 95 DEG C, stirring is to being completely dissolved；The hydrochloric acid for adding that 10 grams of glutaraldehydes and 20 grams of concentration are 37% after normal temperature is cooled to,
Stir, (2) weigh 1 gram of 5- amino-1-hydroxyethyl pyrazoles and be added in the solution obtained by (1) again stirs to well mixed；
Second step：Nonwoven layer, polysulfone supporting layer and the aramid layer set gradually, wherein the polysulfone supporting layer
Preparation process is specially：Weigh 80 grams of polysulfone resin (PSF), 370 grams of N,N-dimethylformamide (DMF) and polyethylene glycol
200 50 grams of (PEG200), is hybridly prepared into 500 grams of solution；6h is stirred at 75 DEG C, dispersed casting solution is configured to；
Casting solution is spread evenly across on non-woven fabrics after filtering, vacuum outgas on knifing machine, and wet-film thickness is 180 μm, at room temperature
Evaporate after 3s, gel solidification film forming in 10 DEG C of ultra-pure water of immersion, after diaphragm is fully cured by normal-temperature water, finally film is existed
3min is handled in 75 DEG C of water, polysulfones support basic unit is obtained；
The setting up procedure of the aramid layer is specially：Weigh 240 grams of m-phenylene diamine (MPD), 88 grams of triethylamine, camphorsulfonic acid 184
Gram and 8 grams of dodecyl sodium sulfate be dissolved in 7480 grams of deionized waters, be uniformly mixing to obtain polyamines aqueous phase solution；By 8 grams
Pyromellitic trimethylsilyl chloride is dissolved into 7992 grams of n-hexanes, is uniformly mixing to obtain acyl chlorides oil-phase solution；First by polysulfone supporting layer with it is many
Amine aqueous phase solution contacts 25s, and unnecessary solution is removed with rubber rollers, and many ammonia solution layers are formed on polysulfone supporting layer surface；Again
Obtained polysulfone supporting layer is contacted into 20s with acyl chlorides oil-phase solution, the remaining oil-phase solution on surface is removed, aramid layer is formed,
Obtain the first matrix；
3rd step：The antipollution solution prepared in the step one is coated in the aramid layer in first matrix
It is upper to be kept for 10 seconds, unnecessary antipollution solution is removed, the first matrix for being finally coated with antipollution solution is put into 80 DEG C of baking
10 minutes are incubated in case, antipollution polyamide composite film is obtained.
The tandem of the first step and second step can be exchanged according to the actual requirements in above-mentioned steps.
Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent crosslink the structural formula of the cross-linked polymer of gained
It is as follows：
Wherein m+n=1, m>0, n>0.
The surface electron microscope of above-mentioned polyamide composite film refers to Fig. 1.
Above-mentioned polyamide composite film is tested, is specially：Diaphragm is taken to be tested on cross-current type diaphragm monitor station,
The 2000ppmNaCl aqueous solution, operating pressure are to enter under 225psi, the test condition that temperature is 25 DEG C and pH value is 7.0 or so
Row test, acquired results are shown in Table 1.
The electron microscope (Fig. 1) of the antipollution polyamide composite film (embodiment 1) obtained from technical solution of the present invention is with passing
The contrast of the electron microscope (Fig. 2) of the polyamide composite film (comparative example) of system can be seen that antipollution polyamide of the present invention and answer
The surface for closing film (embodiment 1) is thicker more smooth than the surface of traditional polyamide composite film (comparative example), therefore, this hair
The antipollution polyamide composite film that bright technical scheme is obtained is more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 1) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Embodiment 2：
A kind of antipollution polyamide composite film, difference from Example 1 is：
The broad spectrum antimicrobial agent containing hydroxyalkyl selects 4,5- diaminostilbenes-(2- ethoxys) pyrazoles.
Above-mentioned polyamide composite film is subjected to test acquired results and is shown in Table 1.
Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent crosslink the structural formula of the cross-linked polymer of gained
It is as follows：
Wherein m+n=1, m>0, n>0.
Than traditional polyamide composite film, (contrast is implemented on the surface of antipollution polyamide composite film (embodiment 2) of the present invention
Example) surface it is thicker more smooth, more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 2) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Embodiment 3：
A kind of antipollution polyamide composite film, difference from Example 1 is：The broad-spectrum antiseptic containing hydroxyalkyl
1,3- dihydroxymethyl -5,5- DMHs are selected in agent.
Above-mentioned polyamide composite film is subjected to test acquired results and is shown in Table 1.Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer with
And crosslinking agent crosslink gained cross-linked polymer structural formula it is as follows：
Wherein m+n=1, m>0, n>0.
Than traditional polyamide composite film, (contrast is implemented on the surface of antipollution polyamide composite film (embodiment 3) of the present invention
Example) surface it is thicker more smooth, more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 3) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Embodiment 4：
A kind of antipollution polyamide composite film, difference from Example 1 is：
The broad spectrum antimicrobial agent containing hydroxyalkyl selects 1- methylol -5,5- DMHs.
Above-mentioned polyamide composite film is subjected to test acquired results and is shown in Table 1.
Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent crosslink the structural formula of the cross-linked polymer of gained
It is as follows：
Wherein m+n=1, m>0, n>0.
Than traditional polyamide composite film, (contrast is implemented on the surface of antipollution polyamide composite film (embodiment 4) of the present invention
Example) surface it is thicker more smooth, more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 4) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Embodiment 5：
A kind of antipollution polyamide composite film, difference from Example 1 is：
The broad spectrum antimicrobial agent containing hydroxyalkyl selects 1,3- dihydroxy ethyl -5,5- DMHs.
Above-mentioned polyamide composite film is subjected to test acquired results and is shown in Table 1.
Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent crosslink the structural formula of the cross-linked polymer of gained
It is as follows.
Than traditional polyamide composite film, (contrast is implemented on the surface of antipollution polyamide composite film (embodiment 5) of the present invention
Example) surface it is thicker more smooth, more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 5) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Wherein m+n=1, m>0, n>0.
Embodiment 6：
A kind of antipollution polyamide composite film, difference from Example 1 is：
The broad spectrum antimicrobial agent containing hydroxyalkyl selects 5- amino-1-hydroxyethyls pyrazoles and 1,3- dihydroxymethyl -5,
5- DMHs, its consumption is respectively：0.5 gram of -1 hydroxyethyl pyrazole of 5- amino is weighed, 1,3- dihydroxymethyls -5,5- bis- are weighed
0.5 gram of methyl hydantoin.
Above-mentioned polyamide composite film is subjected to test acquired results and is shown in Table 1.
Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent crosslink the structural formula of the cross-linked polymer of gained
It is as follows：
Wherein m+n=1, m>0, n>0.
Than traditional polyamide composite film, (contrast is implemented on the surface of antipollution polyamide composite film (embodiment 6) of the present invention
Example) surface it is thicker more smooth, more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 6) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Embodiment 7：
A kind of antipollution polyamide composite film, difference from Example 1 is：
The broad spectrum antimicrobial agent containing hydroxyalkyl selects 5- amino-1-hydroxyethyls pyrazoles, 4,5- diaminostilbenes-(2- hydroxyls
Ethyl) pyrazoles, 1,3- dihydroxymethyl -5,5- DMHs, 1- methylol -5,5- DMHs and 1,3- dihydroxy second
Base -5,5- DMH, its consumption is respectively：The hydroxyethyl pyrazole of 5- amino -1,4,5- diaminostilbenes-(2- hydroxyls are weighed respectively
Ethyl) pyrazoles, 1,3- dihydroxymethyl -5,5- DMHs, 1- methylol -5,5- DMHs and 1,3- dihydroxy second
Each 0.2 gram of base -5,5- DMHs.
Above-mentioned polyamide composite film is subjected to test acquired results and is shown in Table 1.
Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent crosslink the structural formula of the cross-linked polymer of gained
It is as follows：
Wherein m+n=1, m>0, n>0.
Than traditional polyamide composite film, (contrast is implemented on the surface of antipollution polyamide composite film (embodiment 7) of the present invention
Example) surface it is thicker more smooth, more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 7) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Embodiment 8：
A kind of antipollution polyamide composite film, difference from Example 1 is：
The broad spectrum antimicrobial agent containing hydroxyalkyl selects 1,3- dihydroxymethyl -5,5- DMHs, its consumption difference
It is：Weigh 1.0 grams of 1,3- dihydroxymethyl -5,5- DMHs；The hydrophilic polymer selects polyvinyl alcohol, polyethylene glycol
And polyethyleneimine, wherein the degree of polymerization of the polyvinyl alcohol is 1400, its alcoholysis degree is 99%；Point of the polyethylene glycol
Son amount is 20000；The molecular weight of the polyethyleneimine is 10000；Its consumption is：Weigh polyvinyl alcohol, polyethylene glycol and
Each 1.0 grams of polyethyleneimine.
Above-mentioned polyamide composite film is subjected to test acquired results and is shown in Table 1.
Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent exist and 80 DEG C in deionized water and catalyst
At a temperature of crosslink gained cross-linked polymer structural formula it is as follows：
Wherein m+n+o=1, m>0, n>0, o>0.
Than traditional polyamide composite film, (contrast is implemented on the surface of antipollution polyamide composite film (embodiment 8) of the present invention
Example) surface it is thicker more smooth, more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 8) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Embodiment 9：
A kind of antipollution polyamide composite film, difference from Example 1 is：
The broad spectrum antimicrobial agent containing hydroxyalkyl selects 1,3- dihydroxymethyl -5,5- DMHs and 1,3- dihydroxies
Ethyl -5,5- DMH, its consumption is respectively：Weigh 1,3- dihydroxymethyl -5,5- DMHs and 1,3- dihydroxies
Each 1.0 grams of ethyl -5,5- DMHs；The hydrophilic polymer selects polyvinyl alcohol, polyethylene glycol and polyethyleneimine
Amine, wherein the degree of polymerization of the polyvinyl alcohol is 1400, its alcoholysis degree is 99%；The molecular weight of the polyethylene glycol is 20000；
The molecular weight of the polyethyleneimine is 10000；Its consumption is：Weigh polyvinyl alcohol, polyethylene glycol and polyethyleneimine each
1.0 gram.
Above-mentioned polyamide composite film is subjected to test acquired results and is shown in Table 1.
Above-mentioned broad spectrum antimicrobial agent, hydrophilic polymer and crosslinking agent exist and 80 DEG C in deionized water and catalyst
At a temperature of crosslink gained cross-linked polymer structural formula it is as follows：
Wherein m+n+o=1, m>0, n>0, o>0.
Than traditional polyamide composite film, (contrast is implemented on the surface of antipollution polyamide composite film (embodiment 9) of the present invention
Example) surface it is thicker more smooth, more resistant to scratch and anti-pollution.
Traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (embodiment 9) are surveyed with pollution
The decay of water flux refers to Fig. 3 to the percent value of the initial water flux of film in test solution test process.
Comparative example：
The step of preparing polyamide composite film in the prior art is as follows：
The first step：The preparation of polyamines aqueous phase solution, be specially：Weigh 240 grams of m-phenylene diamine (MPD), 88 grams of triethylamine, camphor sulphur
8 grams of 184 grams of acid and dodecyl sodium sulfate are dissolved in 7480 grams of water, are uniformly mixing to obtain polyamines aqueous phase solution；
Second step：The preparation of oil-phase solution, be specially：8 grams of pyromellitic trimethylsilyl chlorides are dissolved into 7992 grams of n-hexanes, stirred
Mix and uniformly obtain acyl chlorides oil-phase solution；
3rd step：The preparation of polyamide composite film, be specially：The support membrane prepared is immersed in many obtained by the first step
25 seconds in amine aqueous phase solution, the aqueous phase solution for remaining in support membrane surface is removed with rubber rollers, then immerse the membrane in second step
20 seconds in the acyl chlorides oil-phase solution of gained, the remaining oil-phase solution on surface is removed, then puts it into and 5 points is dried in 80 DEG C of baking ovens
Clock, obtains polyamide composite film.
The surface electron microscope of above-mentioned polyamide composite film refers to Fig. 2.
Above-mentioned polyamide composite film is tested, is specially：Diaphragm is taken to be tested on cross-current type diaphragm monitor station,
In the 2000ppmNaCl aqueous solution, operating pressure be to carry out under the test condition that 225psi, temperature are 25 DEG C, pH value is 7.0 or so
Test, acquired results are shown in Table 1.
The test result for the polyamide composite film that the embodiment 1-9 of table 1 is obtained with comparative example is compared
From table 1, the antipollution polyamide composite film (embodiment 1- embodiments 9) that technical scheme is obtained
Initial salt-stopping rate apparently higher than traditional polyamide composite film (comparative example), and initial water flux is then lower slightly, in pollution
After being run 12 hours in liquid, both salt rejection rates and water flux have declined, wherein traditional polyamide composite film (implemented by contrast
Example) water flux fall be more than antipollution polyamide composite film of the present invention (embodiment 1- embodiments 9)；And from reduction in colony
Situation from the point of view of, antipollution polyamide composite film (embodiment 1- embodiments 9) of the present invention and the (contrast of traditional polyamide composite film
Embodiment) its antimicrobial properties that compare are greatly improved and (are made of conventional reverse osmosis film and complex reverse osmosis membrane of the present invention
Escherichia coli culture experiment is compared acquired results).
The anti-pollution ability that decay to water flux brings evaluated for film with the change of time is membrane for water treatment anti-fouling performance
The common method of evaluation.Fig. 3 is that traditional polyamide composite film (comparative example) and present invention gained polyamide composite film (are implemented
Example 1- embodiments 9) decay of water flux in Contamination measurement liquid test process is used to the percent value of the initial water flux of film.From Fig. 3
In as can be seen that the present invention gained polyamide composite film (embodiment 1- embodiments 9) flux decline than traditional polyamide be combined
Slowly, and after pure water is cleaned, water flux recovers fast to film (comparative example).This explanation present invention gained polyamide composite film
(embodiment 1- embodiments 9) has more preferable anti-fouling performance than traditional polyamide composite film (comparative example), thus, this hair
Bright gained polyamide composite film (embodiment 1- embodiments 9) has good anti-fouling performance, especially microbial contamination resistance
Energy.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (9)
1. a kind of antipollution polyamide composite film, it is characterised in that：Including the nonwoven layer set gradually, polysulfone supporting layer, gather
Amide layer and anti-pollution layer；
The anti-pollution layer is included by the broad spectrum antimicrobial agent containing hydroxyalkyl, hydrophilic polymer and crosslinking agent in water and catalysis
Agent exist and 50-120 DEG C under the conditions of carry out cross-linking reaction obtained from antibacterial hydrophilic crosslinked polymer；
The broad spectrum antimicrobial agent is triazole type, dicarboximide class, morpholine class, thiocarbamates, phenylpyrrole class, benzene
At least one of and imidazoles, pyrazoles, glycolylurea class, miazines and pyroles；It is calculated in mass percent, the wide spectrum resists
The content of microbial inoculum is 0.01-10%.
2. antipollution polyamide composite film according to claim 1, it is characterised in that：The broad spectrum antimicrobial agent is 5- ammonia
Base -1- hydroxyethyl pyrazoles, 4,5- diaminostilbenes-(2- ethoxys) pyrazoles, 1,3- dihydroxymethyl -5,5- DMHs, 1- hydroxyls
At least one of methyl -5,5- DMHs and 1,3- dihydroxy ethyl -5,5- DMHs；The broad spectrum antimicrobial agent
Content be 0.1-3%.
3. antipollution polyamide composite film according to claim 1, it is characterised in that：The hydrophilic polymer is poly- second
At least one of enol, polyethylene glycol and polyethyleneimine；It is calculated in mass percent, the content of the hydrophilic polymer
For 0.01-5%.
4. antipollution polyamide composite film according to claim 3, it is characterised in that：The hydrophilic polymer is polymerization
The polyethylene glycol that degree is 200-4000 and alcoholysis degree is 75-100% polyvinyl alcohol, mean molecule quantity are 200-100000 with
And mean molecule quantity is at least one of 300-80000 polyethyleneimine；It is calculated in mass percent, the hydrophilic polymer
The content of thing is 0.1-2%.
5. the antipollution polyamide composite film according to claim 1 or 3, it is characterised in that：The crosslinking agent be glyoxal,
Any one in butanedial, hexandial, glutaraldehyde and boric acid；The catalyst be hydrochloric acid, nitric acid, phosphoric acid, formic acid and
Any one in acetic acid.
6. antipollution polyamide composite film according to claim 5, it is characterised in that：The thickness of the aramid layer is
50-300nm, the thickness of the anti-pollution layer is 20-200nm；The catalyst use concentration for 37% hydrochloric acid.
7. a kind of preparation method of antipollution polyamide composite film, it is characterised in that：Comprise the following steps：
Step one：Antipollution solution is prepared, is specially：Broad spectrum antimicrobial agent containing hydroxyalkyl is dissolved in containing hydrophilic polymer
The aqueous solution in；Add catalyst 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 the step one is coated on the aramid layer in 50-120 DEG C of condition
Lower generation cross-linking reaction formation anti-pollution layer, produces antipollution polyamide composite film.
8. the preparation method of antipollution polyamide composite film according to claim 7, it is characterised in that：The polysulfones support
Layer and the setting up procedure of aramid layer are specially：First by polysulfone supporting layer with containing at least two reactive amino compounds
Many ammonia solution contacts, unnecessary solution is removed with rubber rollers, and many ammonia solution layers are formed on polysulfone supporting layer surface；It will obtain again
Polysulfone supporting layer contact to form aramid layer with the solution of acid chloride at least containing two reactive acid chloride groups；
In the step 3 reaction is crosslinked under the conditions of temperature is 60-100 DEG C；
The thickness of the aramid layer is 50-300nm, and the thickness of the anti-pollution layer is 20-200nm；
The hydrophilic polymer is preferably at least one of polyvinyl alcohol, polyethylene glycol and polyethyleneimine；
The broad spectrum antimicrobial agent is triazole type, dicarboximide class, morpholine class, thiocarbamates, phenylpyrrole class, benzene
At least one of and imidazoles, pyrazoles, glycolylurea class, miazines and pyroles；
It is calculated in mass percent, the content of the hydrophilic polymer is 0.01-5%；
It is calculated in mass percent, the content of the broad spectrum antimicrobial agent is 0.01-10%；
The crosslinking agent is any one in glyoxal, butanedial, hexandial, glutaraldehyde and boric acid；
The catalyst is any one in hydrochloric acid, nitric acid, phosphoric acid, formic acid and acetic acid.
9. the preparation method of antipollution polyamide composite film according to claim 8, it is characterised in that：
In the step 3 temperature be 80 DEG C；
The hydrophilic polymer uses the polyvinyl alcohol that the degree of polymerization is 75-100% for 200-4000 and alcoholysis degree, mean molecule
The polyethylene glycol and mean molecule quantity that amount is 200-100000 are at least one of 300-80000 polyethyleneimine；
The broad spectrum antimicrobial agent is 5- amino-1-hydroxyethyls pyrazoles, 4,5- diaminostilbenes-(2- ethoxys) pyrazoles, 1,3- bis-
Methylol -5,5- DMHs, 1- methylol -5,5- DMHs and 1,3- dihydroxy ethyl -5,5- DMHs
At least one of；
It is calculated in mass percent, the content of the hydrophilic polymer is 0.1-2%；
It is calculated in mass percent, the content of the broad spectrum antimicrobial agent is 0.1-3%；
The catalyst use concentration for 37% hydrochloric acid.
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| CN106621851A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Antibacterial reverse osmosis composite membrane and preparation method and application thereof |
| CN105561801B (en) * | 2015-12-19 | 2018-04-27 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of the reverse osmosis pollution-resistant membrane of high-performance |
| CN107303470B (en) * | 2016-04-20 | 2020-07-24 | 中国石油化工股份有限公司 | Antibacterial reverse osmosis composite membrane, preparation method and application thereof |
| CN107970776A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application |
| CN107983158B (en) * | 2016-10-26 | 2021-02-05 | 中国石油化工股份有限公司 | Antibacterial composite nanofiltration membrane and preparation method thereof |
| CN107899434A (en) * | 2017-09-25 | 2018-04-13 | 浙江理工大学 | A kind of preparation method of tight type chlorine-resistant composite nanometer filtering film |
| CN107638805B (en) * | 2017-11-03 | 2019-11-22 | 宁波日新恒力科技有限公司 | A kind of reverse osmosis membrane preparation method that graphene oxide/polyvinyl alcohol is coating modified |
| CN108159894A (en) * | 2018-01-17 | 2018-06-15 | 浙江工业大学 | A kind of preparation method of polyvinyl alcohol composite nanometer filtering film |
| CN114432900B (en) * | 2020-11-04 | 2023-03-21 | 沃顿科技股份有限公司 | Preparation method of anti-pollution composite reverse osmosis membrane and anti-pollution composite reverse osmosis membrane prepared by same |
| CN112717720B (en) * | 2020-12-25 | 2022-05-20 | 湖南澳维科技股份有限公司 | Pollution-resistant polyamide composite membrane and preparation method thereof |
| CN114618313B (en) * | 2021-12-13 | 2022-12-16 | 宁波水艺膜科技发展有限公司 | High-flux anti-pollution reverse osmosis composite membrane and preparation method thereof |
| CN114438665B (en) * | 2022-01-28 | 2023-04-25 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial non-woven fabric and preparation method thereof |
| CN115850646B (en) * | 2022-12-30 | 2024-01-26 | 嘉兴学院 | Waterborne polyurethane for marine antifouling and preparation method thereof |
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| AU2007200609B2 (en) * | 2007-02-13 | 2008-11-20 | Saehan Industries Incorporation | Selective membrane having a high fouling resistance |
| CN101462024A (en) * | 2008-12-24 | 2009-06-24 | 北京时代沃顿科技有限公司 | Composite reverse osmosis membrane with high-intensity anti-pollution layer and preparation method thereof |
| CN101497002A (en) * | 2009-01-14 | 2009-08-05 | 大连理工大学 | Method for preparing anti-pollution chitosan-nonwoven cloth composite porous filter membrane |
| CN101695636B (en) * | 2009-11-04 | 2012-06-20 | 天津大学 | Grafted modified aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
| CN102580579B (en) * | 2012-03-12 | 2014-06-04 | 山东九章膜技术有限公司 | Inorganic pollution resistance antibacterial reverse osmosis membrane and preparation method thereof |
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