CN108939932A - A kind of preparation method of high-performance aromatic polyamides composite membrane - Google Patents
A kind of preparation method of high-performance aromatic polyamides composite membrane Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of high-performance aromatic polyamides composite membrane, and the density of the high-performance aromatic polyamides composite film surface grafting PEO chain, quaternary ammonium cation and salicylide is high, and film surface hydrophily is high；Film surface has not only been grafted the functional group, but also fragrant diamides structural unit is accessed, its chemical property and the fragrant diamides structural unit in film aromatic polyamides active layer are similar, can be used as expendable material in advance in seawater residual chlorine or chlorine oxonium compound generate chemical reaction, residual chlorine or chlorine oxonium compound effectively in prevention seawater ensure the permanent stability of membrane structure to the chemical depletion of film aromatic polyamides active layer；The salicylide monolayer being grafted in film surface is uniformly distributed, can heavy metal ion in high efficiency filter adsorbing seawater, generate antibacterial and kill livestock function, there is positive effect to the cleaning for guaranteeing film surface.
Description
Technical field
The present invention relates to a kind of preparation method of high-performance aromatic polyamides composite membrane, in particular to surface grafting PEG chain,
The preparation method of the high-performance aromatic polyamides composite membrane of quaternary ammonium cation and salicylide functional group is applied to sea water desalination work
Skill belongs to functional polymer material field.
Background technique
Aromatic polyamides composite membrane (aromatic polyamides thin film composite membrane,
APA-TFC membrane) be deposited on by one layer of ultra-thin aromatic polyamide membrane porous polysulfones or polyether sulfone support counterdie on it is compound
Made of, aromatic polyamides are referred to using m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride as the polymer of monomer.The water flux of such film
Greatly, salt rejection rate is high, oneself becomes the main product to desalinize seawater.However aromatic polyamides composite membrane is in recent two decades use process
Thorny problem be exactly marine organisms to the pollution of film and Active Chlorine to the chemical degradation of film.What the film marine biological polution referred to
Seawater microorganism the adherency of composite film surface, growth, breeding and form abnormal obstinate biosphere, it is difficult to manual cleaning,
Seriously affect the working efficiency of composite membrane；In order to solve in desalting process marine microorganism to aromatic polyamides composite membrane
Biological pollution, it is necessary to which logical chlorine pretreatment is carried out to seawater.However, since Micro Amounts of Chlorine remaining in seawater and oxychloride are poly- to fragrance
The chemical depletion of amide composite membrane, and substantially reduce service performance and the service life of aromatic polyamides composite membrane.Therefore, how both
The compound fouling membrane of aromatic polyamides can be efficiently controlled and be mitigated, ensures that the chemical stability of aromatic polyamides composite membrane,
The always important subject of aromatic polyamides technical field of membrane.
Since more than 20 years, surface depolluting properties are high, chlorine oxidative stability is high, surface hydrophilicity is high, water in order to obtain by people
The aromatic polyamides composite membrane of the big equal excellent combination properties of flux, aromatic polyamides composite film surface is modified be effectively,
Fast, simply, flexible method, mainly have: (1) surface coating is covered with paint, lacquer, colour wash, etc., (2) surface aggregate deposition, (3) surface graft modification,
Wherein film surface coating or grafting water polyethylene glycol (referred to as PEG), polyacrylic acid, polyacrylamide, quaternary ammonium salt, chlorine sea
Cause, amphoteric ion polymer brush, graphene oxide or carbon nanotube etc. all produce the anti-pollution and anti-chlorine stability that improve film
Positive effect is given birth to.But it is poor using the uniformity that the above method modifies film surface, the blocking of membrane micropore gap is easily caused,
Transparency reduces；In addition the Functional group density that film surface introduces is small, causes film surface hydrophily not high, and water flux changes not
Greatly；There are also being carried out in graft copolymerization modification to film surface, as monomer homopolymerization caused by monomer raw material waste it is serious；
The protrusion defect of last existing process for modifying surface is to the performance improvement of aromatic polyamides composite membrane be it is monistic, without complete
The comprehensive performance of orientation raising film.
For the defect of existing aromatic polyamides composite film surface modification technique and graft-modification method, the present inventor was once
It proposes equably " to plant the structural unit containing quaternary ammonium salt and salicylide functional group " on the surface of the film by chemical reaction
Method (referring to CN103349922B).Its principle is killed livestock using the sterilizing of quaternary ammonium salt and salicylide functional group different mechanisms
The effect of heavy metal ion in effect, selective complexation adsorbing seawater generates and cooperates with efficient anti-marine biofouling function, protects
Demonstrate,prove the cleaning of film surface；Secondly, aromatic polyamides composite film surface salicylide functional group abundant with it is residual in pre-treating seawater
The chemical reaction for depositing Micro Amounts of Chlorine and oxychloride is more quick, prevents the change of remaining Micro Amounts of Chlorine and oxychloride to film in seawater
Destruction is learned, has ensured service performance and the service life of aromatic polyamides composite membrane；Furthermore quaternary ammonium salt on film surface grafting, can
It is beneficial to the water flux for ensureing film to effectively improve the hydrophilicity of film.The extension of time, ocean are used however as film
The problem of biodeterioration, still remains.The present inventor in 2015 modifies newborn virtue further through organic polyamine in CN105251372B
Fragrant polyamide composite film, then with N, N, N- trialkyl-N- (4- hydroxyl -3- aldehyde radical benzyl) ammonium chloride carry out condensation reaction, system
The higher method of the density of film surface grafting schiff base of salicylaldehyde and quaternary ammonium cation is taken, however the hydrophily of film surface changes,
Water flux increases.For the defect of current aromatic polyamides composite membrane Functionalization and method, the present invention provides one kind
The preparation method of high-performance aromatic polyamides composite membrane.
Summary of the invention
The present invention provides a kind of preparation method of high-performance aromatic polyamides composite membrane, the in particular to poly- second two of surface grafting
The preparation method of the high-performance aromatic polyamides composite membrane of alcohol chain, quaternary ammonium cation and salicylide functional group；It is logical first
Cross the exposed acid chloride groups of newborn aromatic polyamides composite film surface and two hydrocarbon amino-polyethyleneglycols (also commonly referred to as monoamine bases of end
Polyethylene glycol, end amido PEG) esterification is carried out, the aromatic polyamides composite membrane of surface grafting end tertiary amine groups PEG chain is made；
Secondly, the addition reaction of the aromatic polyamides composite membrane and diisocyanate of the surface grafting end tertiary amine groups PEG chain, is made table
The aromatic polyamides composite membrane of face grafting end tertiary amine groups PEG chain and isocyanate group；Furthermore surface grafting end tertiary amine groups PEG chain
With the aromatic polyamides composite membrane of isocyanate group respectively with N, surface is made in bis- hydrocarbon amino propylamine of N- dialkyl ethanol amine or 3-
It is grafted the aromatic polyamides composite membrane of end tertiary amine groups PEG chain and tertiary amine groups；Finally, by surface grafting end tertiary amine groups PEG chain and
The aromatic polyamides composite membrane of tertiary amine groups is reacted with the quaternization of 5- chloromethyl salicylaldehyde, and surface grafting PEG chain, quaternary ammonium is made
The high-performance aromatic polyamides composite membrane of cation and salicylide.
The beneficial effects of the invention are as follows aromatic polyamides composite film surface grafting PEG chain, quaternary ammonium cation and salicylides
Density is increased substantially compared to CN103349922B or CN105251372B；Film surface hydrophily also accordingly increases substantially；Film
Surface has not only been grafted bigcatkin willow aldehyde group, but also has accessed fragrant diamides based structures unit, chemical property and film fragrance
Fragrant diamides based structures unit class in polyamide active layer is same, can be used as expendable material in advance with the residual chlorine in seawater
Or chlorine oxonium compound generates chemical reaction, effectively the residual chlorine in prevention seawater or chlorine oxonium compound are to aromatic polyamides composite membrane
The chemical depletion of active layer ensures the permanent stability of aromatic polyamides composite membrane self structure；The bigcatkin willow being grafted in film surface
Aldehyde monolayer is uniformly distributed, can heavy metal ion in high efficiency filter adsorbing seawater, generate and quaternary ammonium cation and water
The antibacterial of poplar aldehyde collaboration is killed livestock function, has positive effect to the cleaning for guaranteeing film surface.
The preparation method of high-performance aromatic polyamides composite membrane provided by the invention is following specific described:
The preparation method of the aromatic polyamides composite membrane of step 1 surface grafting end tertiary amine groups polyglycol chain
It is 1.5~25% that the newborn aromatic polyamides composite membrane that acid chloride groups are contained on surface, which is immersed in mass percentage concentration,
Two hydrocarbon amino-polyethyleneglycols solution of end in, control the temperature of the two hydrocarbon amino-polyethyleneglycols solution of end 60~90 DEG C it
Between, after esterification 2~24 hours, pull film out, successively using ethyl alcohol, mass percent be 10% aqueous sodium carbonate and
Deionized water washs film to neutrality, and then desciccator diaphragm, is made the aromatic polyamides composite membrane of surface grafting end tertiary amine groups PEG chain,
1. referring to reaction schematic.
The newborn aromatic polyamides composite membrane that wherein acid chloride groups are contained on the surface is according to J.Membr.Sci.428
Disclosed in (2013) 4 03-409 or J.Membr.Sci.457 (2014) 88-97, CN103349922B or CN105251372B
Method and steps, using m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride as monomer, by micropore polysulfones support membrane or micropore polyether sulfone
Made from the polymerization of support membrane surface interface；
The chemical structure of the two hydrocarbon amino-polyethyleneglycols of end is by shown in general formula (A):
Wherein the R1 in the general formula (A) and R2 is respectively selected from the alkyl of C1~C18, and n is selected from 3~3000 integer；
The two hydrocarbon amino-polyethyleneglycols solution of end refers to dissolving the two hydrocarbon amino-polyethyleneglycols of end in a solvent
It is obtained；The dosage of the two hydrocarbon amino-polyethyleneglycols solution of end is that the newborn aromatic polyamides that acid chloride groups are contained on surface are compound
1~10 times of film quality；
The solvent refer to ethyl acetate, acetone, 1,4- dioxane, tetrahydrofuran, triethylamine, triethylene diamine,
One or both of N- methyl morpholine, pyridine, 4-dimethylaminopyridine, 1,2- dichloroethanes, carbon tetrachloride or chloroform with
On；The preparation method of step 2 surface grafting end tertiary amine groups polyglycol chain and the aromatic polyamides composite membrane of isocyanate group
It weighs diisocyanate and organotin dissolution in organic solvent, diisocyanate solution, control described two is made
Diisocyanate mass percentage concentration in isocyanate solution is 1.5~25%, and the dosage of the organotin is diisocyanate
The 0.05~5% of ester quality；The diisocyanate solution temperature is controlled between 0~90 DEG C, surface is made in step 1 and is connect
The aromatic polyamides composite membrane of branch end tertiary amine groups PEG chain is immersed in the diisocyanate solution, is reacted 0.5~8 hour
Afterwards, it pulls film out, with chloroform or ethyl acetate purification membrane, the fragrance of surface grafting end tertiary amine groups PEG chain and isocyanate group is made
Polyamide composite film, 2. referring to reaction schematic.
Wherein the diisocyanate is selected from paraphenylene diisocyanate (PPDI), m-benzene diisocyanate (MPDI), toluene
Diisocyanate (TDI), hexamethylene -1,4- diisocyanate (CHDI), diphenyl methane -4,4 '-diisocyanate (MDI),
1,6- hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride -4,4 '-diisocyanate
(H12MDI), one of trimethylhexane diisocyanate (TMDI) or durol xylene diisocyanate (TMXDI).
The organotin refers to dibutyltin dilaurate, stannous octoate, stannous oxalate, two maleic acid of dialkyl group
Tin, two (dodecyl sulphur) one of dibutyl tins or dibutyltin diacetate；
The organic solvent refers to ethyl acetate, propyl acetate, butyl acetate, acetone, 1,4- dioxane, tetrahydro furan
It mutters, one or more of glycol dimethyl ether, ethylene glycol diethyl ether or 1,2- dichloroethanes；
The preparation method of step 3 surface grafting end tertiary amine groups PEG chain and the aromatic polyamides composite membrane of tertiary amine groups
N is weighed, N- dialkyl ethanol amine or bis- hydrocarbon amino propylamine of 3-, which are dissolved in solvent, is made ertiary amine solution, described in control
N, N- dialkyl ethanol amine or bis- hydrocarbon amino propylamine mass percentage concentration of 3- are 1.5~25%, control the ertiary amine solution temperature
Between 25~90 DEG C, the aromatic polyamides that surface grafting end tertiary amine groups PEG chain and isocyanate group is made in step 2 are compound
After film immersion reacts 0.5~8 hour in the ertiary amine solution, film is pulled out, with ethanol washing film, then baked film, is made table
The aromatic polyamides composite membrane of end tertiary amine groups PEG chain and tertiary amine groups is contained in face, 3. referring to reaction schematic.
The chemical structure of the wherein N, N- dialkyl ethanol amine is by shown in general formula (B):
The wherein R in the general formula (B)1And R2It is respectively selected from C1~C18Alkyl.
The chemical structure of the bis- hydrocarbon amino propylamine of 3- is by shown in general formula (C):
The wherein R in the general formula (C)1And R2It is respectively selected from C1~C18Alkyl.
The dosage of the ertiary amine solution is the fragrant polyamides of surface grafting end tertiary amine groups, polyglycol chain and isocyanate group
1~10 times of the compound film quality of amine；
The solvent refer to ethyl acetate, acetone, 1,4- dioxane, tetrahydrofuran, triethylamine, triethylene diamine,
One or both of N- methyl morpholine, pyridine, 4-dimethylaminopyridine, 1,2- dichloroethanes, carbon tetrachloride or chloroform with
On；The preparation of the high-performance aromatic polyamides composite membrane of step 4 surface grafting polyglycol chain, quaternary ammonium cation and salicylide
Method
It weighs the dissolution of 5- chloromethyl salicylaldehyde in a solvent, 5- chloromethyl salicylaldehyde solution is made, controls the 5- chloromethane
The mass percentage concentration of base salicylide solution is 3~30%；5- chloromethyl salicylaldehyde solution temperature is controlled to -5~65 DEG C, will be walked
End tertiary amine groups PEG chain is contained on surface made from rapid three and the aromatic polyamides composite membrane of tertiary amine groups is immersed in the 5- chloromethyl water
In poplar aldehyde solution, reaction 2~12 hours after, pull film out, wash, drying, obtain surface grafting polyglycol chain, quaternary ammonium sun from
The high-performance aromatic polyamides composite membrane of son and salicylide functional group, 4. referring to reaction schematic.
Wherein the dosage of the 5- chloromethyl salicylaldehyde is that the fragrance of surface grafting end tertiary amine groups, PEG chain and tertiary amine groups is poly-
The 3~30% of the compound film quality of amide.
The solvent refer to ethyl acetate, propyl acetate, butyl acetate, acetone, 1,4- dioxane, tetrahydrofuran,
One or more of glycol dimethyl ether, ethylene glycol diethyl ether or 1,2- dichloroethanes；
High-performance chlorine aromatic polyamides composite membrane provided by the invention has the feature that
1. the surface hydrophilicity of high-performance poly aromatic amide composite membrane provided by the invention is high, anti-marine biofouling performance
Height, chlorine-resistant oxygen ability are strong, and sea water desalination runnability is stablized lasting.
2. the raw material for preparing high-performance poly aromatic amide composite membrane provided by the invention is commercial goods, preparation method mostly
It is simple and easy, it is easy to industrialize.
Detailed description of the invention
Fig. 1 be reaction schematic 1.；
Fig. 2 be reaction schematic 2.；
Fig. 3 be reaction schematic 3.；
Fig. 4 be reaction schematic 4..
Specific embodiment
By following example to the preparation method of high-performance aromatic polyamides composite membrane provided by the invention furtherly
Bright, its object is to more fully understand the contents of the present invention.
The preparation of 1 high-performance aromatic polyamides composite membrane (1) of embodiment
The preparation of the aromatic polyamides composite membrane of step 1 surface grafting dimethylamino PEG chain
According to Journal of Membrane Science 428 (2013) 403-409 or Journal of Membrane
Method and operating procedure disclosed in Science 457 (2014) 88-97, CN103349922B or CN105251372B,
10*10cm square micropore polysulfones supports on membrane surface, passes through the interfacial polymerization of m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride, system
The newborn aromatic polyamides composite membrane that acid chloride groups are contained on surface is obtained, the newborn aromatic polyamides that acid chloride groups are contained on surface are answered
Close the 1,4- that film immersion is 5.5% in (also referred to as DMA-PEG-600) mass percentage concentration of dimethylamino polyethylene glycol -600
In dioxane (20mL) and the 30mL solution of triethylamine (10mL) mixing, temperature control completes esterification after 60~65 DEG C, 6 hours
Reaction, pulls film out, and successively using ethyl alcohol, aqueous sodium carbonate and deionized water washing film to neutrality, desciccator diaphragm, obtained surface is connect
The aromatic polyamides composite membrane of branch dimethylamino PEG chain.
The preparation of step 2 surface grafting dimethylamino PEG chain and the aromatic polyamides composite membrane of isocyanate group
It weighs 6.5 grams of paraphenylene diisocyanate and a small amount of organotin is dissolved in 30mL acetone, be made to benzene diisocyanate
Ester solution, then for controlling temperature at 25~35 DEG C, the aromatic polyamides that surface grafting dimethylamino PEG chain is made in step 1 are compound
Film immersion after reaction 3.5 hours, pulls film out in paraphenylene diisocyanate solution, and using chloroform purification membrane, surface grafting is made
The aromatic polyamides composite membrane of dimethylamino PEG chain and isocyanate group.
The preparation method of the aromatic polyamides composite membrane of step 3 surface grafting dimethylamino PEG chain and dimethylamino
Weigh 10 grams of N, N- dimethylethanolamine is dissolved in 30mL1, and in 4- dioxane, N, N- dimethylethanolamine is made
1,4- dioxane solution；Then the fragrance that surface grafting dimethylamino PEG chain and isocyanate group is made in step 2 is gathered
Amide composite membrane is immersed in N, in Isosorbide-5-Nitrae-dioxane solution of N- dimethylethanolamine, 60~65 DEG C of temperature control after reaction 4 hours,
It pulls film out, successively washs film to neutrality, drying using ethyl alcohol, the aqueous sodium carbonate that mass percent is 10% and deionized water
The aromatic polyamides composite membrane of surface grafting dimethylamino PEG chain and dimethylamino is made in film.
The preparation method of step 4 high-performance aromatic polyamides composite membrane
It weighs 10 grams of 5- chloromethyl salicylaldehydes to be dissolved in 40mL ethyl acetate, 5- chloromethyl salicylaldehyde solution is made；It will
The aromatic polyamides composite membrane of surface grafting dimethylamino PEG chain made from step 3 and dimethylamino be immersed in temperature be 25~
In 30 DEG C of 5- chloromethyl salicylaldehyde solution, after reaction 2 hours, film is pulled out, it is rear to dry with ethyl acetate purification membrane, it obtains
High-performance aromatic polyamides composite membrane (1).
The preparation of 2 high-performance aromatic polyamides composite membrane (2) of embodiment
According to the method and operating procedure of embodiment 1, the paraphenylene diisocyanate in 1 step 2 of embodiment is changed as first
Phenylene diisocyanate, the N in step 3, it is 3- dimethylaminopropylamine that N- dimethylethanolamine, which changes, obtains high-performance fragrance
Polyamide composite film (2).
The preparation of 3 high-performance aromatic polyamides composite membrane (3) of embodiment
According to the method and operating procedure of embodiment 1, the dimethylamino polyethylene glycol -600 in 1 step 1 of embodiment is changed
It is changed to dimethylamino Polyethylene glycol-2000, it is toluene di-isocyanate(TDI), step 3 that the paraphenylene diisocyanate in step 2, which is changed,
In N, N- dimethylethanolamine change be 3- dimethylaminopropylamine, obtain high-performance aromatic polyamides composite membrane (3).
The preparation of 4 high-performance aromatic polyamides composite membrane (4) of embodiment
According to the method and operating procedure of embodiment 1, the dimethylamino polyethylene glycol -600 in 1 step 1 of embodiment is changed
It is changed to dimethylamino Polyethylene glycol-2000, it is toluene di-isocyanate(TDI) that the paraphenylene diisocyanate in step 2, which is changed, is obtained
High-performance aromatic polyamides composite membrane (4).
5 high-performance aromatic polyamides composite membrane (1) of embodiment~(4) performance
High-performance aromatic polyamides composite membrane (1)~(4) in Example 1~4 respectively, according to Journal of
Membrane Science 428 (2013) 403-409 or Journal of Membrane Science 457 (2014) 88-
97, CN103349922B or or CN105251372B disclosed in method, observation high-performance aromatic polyamides composite membrane (1)~
(4) water contact angle θ, water flux and salt rejection rate, as a result details are shown in Table 1.
1 high-performance aromatic polyamides composite membrane (1) of table~(4) performance
The above description is merely a specific embodiment, but the protection scope invented is not limited thereto, any ripe
Know those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all cover
Within the protection scope of invention.
Claims (7)
1. a kind of preparation method of high-performance aromatic polyamides composite membrane, refer to surface grafting polyglycol chain, quaternary ammonium sun from
The preparation method of the aromatic polyamides composite membrane of son and salicylide, it is characterised in that specific preparation step as described below:
The preparation method of the aromatic polyamides composite membrane of step 1 surface grafting end tertiary amine groups polyglycol chain
The newborn aromatic polyamides composite membrane that acid chloride groups are contained on surface is immersed in the end that mass percentage concentration is 1.5~25%
In two hydrocarbon amino-polyethyleneglycols solution, the temperature of the two hydrocarbon amino-polyethyleneglycols solution of end is controlled between 60~90 DEG C, ester
After changing reaction 2~24 hours, film is pulled out, successively using ethyl alcohol, the aqueous sodium carbonate and deionization that mass percent is 10%
Water washing film is to neutrality, and then desciccator diaphragm, is made the aromatic polyamides composite membrane of surface grafting end tertiary amine groups polyglycol chain；
Wherein the two hydrocarbon amino-polyethyleneglycols solution of end refers to dissolving the two hydrocarbon amino-polyethyleneglycols of end in a solvent
It is obtained；The dosage of the two hydrocarbon amino-polyethyleneglycols solution of end is that the newborn aromatic polyamides that acid chloride groups are contained on surface are compound
1~10 times of film quality；
The solvent refers to ethyl acetate, acetone, 1,4- dioxane, tetrahydrofuran, triethylamine, triethylene diamine, N- first
One or more of base morpholine, pyridine, 4-dimethylaminopyridine, 1,2- dichloroethanes, carbon tetrachloride or chloroform；
The preparation method of step 2 surface grafting end tertiary amine groups polyglycol chain and the aromatic polyamides composite membrane of isocyanate group
It weighs diisocyanate and organotin dissolution in organic solvent, diisocyanate solution is made, controls two isocyanide
Diisocyanate mass percentage concentration in acid esters solution is 1.5~25%, and the dosage of the organotin is diisocyanate matter
The 0.05~5% of amount；The diisocyanate solution temperature is controlled between 0~90 DEG C, surface grafting end is made in step 1
The aromatic polyamides composite membrane of tertiary amine groups polyglycol chain is immersed in the diisocyanate solution, is reacted 0.5~8 hour
Afterwards, it pulls film out, with chloroform or ethyl acetate purification membrane, surface grafting end tertiary amine groups polyglycol chain and isocyanate group is made
Aromatic polyamides composite membrane；
The organic solvent refer to ethyl acetate, propyl acetate, butyl acetate, acetone, 1,4- dioxane, tetrahydrofuran,
One or more of glycol dimethyl ether, ethylene glycol diethyl ether or 1,2- dichloroethanes；
The preparation method of step 3 surface grafting end tertiary amine groups polyglycol chain and the aromatic polyamides composite membrane of tertiary amine groups
N is weighed, N- dialkyl ethanol amine or bis- hydrocarbon amino propylamine of 3-, which are dissolved in solvent, is made ertiary amine solution, controls the N, N-
Dialkyl ethanol amine or bis- hydrocarbon amino propylamine mass percentage concentration of 3- are 1.5~25%；The ertiary amine solution temperature is controlled 25
Between~90 DEG C, the aromatic polyamides that surface grafting end tertiary amine groups polyglycol chain and isocyanate group is made in step 2 are compound
After film immersion reacts 0.5~8 hour in the ertiary amine solution, film is pulled out, with ethanol washing film, then baked film, is made table
The aromatic polyamides composite membrane of face grafting end tertiary amine groups polyglycol chain and tertiary amine groups；
Wherein the dosage of the ertiary amine solution is the fragrant polyamides of surface grafting end tertiary amine groups polyglycol chain and isocyanate group
1~10 times of the compound film quality of amine；
The solvent refers to ethyl acetate, acetone, 1,4- dioxane, tetrahydrofuran, triethylamine, triethylene diamine, N- first
One or more of base morpholine, pyridine, 4-dimethylaminopyridine, 1,2- dichloroethanes, carbon tetrachloride or chloroform；
The preparation method of the high-performance aromatic polyamides composite membrane of step 4 surface grafting quaternary ammonium cation and salicylide
It weighs the dissolution of 5- chloromethyl salicylaldehyde in a solvent, 5- chloromethyl salicylaldehyde solution is made, controls the 5- chloromethyl water
The mass percentage concentration of poplar aldehyde solution is 3~30%；5- chloromethyl salicylaldehyde solution temperature is controlled to -5~65 DEG C, by step 3
Surface grafting end tertiary amine groups polyglycol chain obtained and the aromatic polyamides composite membrane of tertiary amine groups are immersed in the 5- chloromethyl
It in salicylide solution, after reaction 2~12 hours, pulls film out, washs, drying obtains surface grafting polyglycol chain, quaternary ammonium sun
The high-performance aromatic polyamides composite membrane of ion and salicylide functional group；
Wherein the dosage of the 5- chloromethyl salicylaldehyde is poly- for surface grafting end tertiary amine groups polyglycol chain and the fragrance of tertiary amine groups
The 3~30% of the compound film quality of amide；
The solvent refers to ethyl acetate, propyl acetate, butyl acetate, acetone, 1,4- dioxane, tetrahydrofuran, second two
One or more of diethylene glycol dimethyl ether, ethylene glycol diethyl ether or 1,2- dichloroethanes.
2. a kind of preparation method of high-performance aromatic polyamides composite membrane according to claim 1, it is characterised in that the table
The newborn aromatic polyamides composite membrane that acid chloride groups are contained in face is using m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride as monomer, by micro-
Made from hole polysulfones support membrane or the polymerization of micropore polyether sulfone support membrane surface interface.
3. a kind of preparation method of high-performance aromatic polyamides composite membrane according to claim 1, it is characterised in that the end
The chemical structure of two hydrocarbon amino-polyethyleneglycols is by shown in general formula (A):
R in its formula of (A)1And R2It is respectively selected from C1~C18Alkyl, n be selected from 3~3000 integer.
4. a kind of preparation method of high-performance aromatic polyamides composite membrane according to claim 1, it is characterised in that described two
Isocyanates is selected from paraphenylene diisocyanate, m-benzene diisocyanate, toluene di-isocyanate(TDI), hexamethylene -1,4- diisocyanate
Ester, diphenyl methane -4,4 '-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl first
One of alkane -4,4 '-diisocyanate, trimethylhexane diisocyanate or durol xylene diisocyanate.
5. a kind of preparation method of high-performance aromatic polyamides composite membrane according to claim 1, it is characterised in that:
The organotin refers to dibutyltin dilaurate, stannous octoate, stannous oxalate, two maleic acid tin of dialkyl group, two
(dodecyl sulphur) one of dibutyl tin or dibutyltin diacetate.
6. a kind of preparation method of high-performance aromatic polyamides composite membrane according to claim 1, it is characterised in that the N,
The chemical structure of N- dialkyl ethanol amine is by shown in general formula (B):
The wherein R in the general formula (B)1And R2It is respectively selected from C1~C18Alkyl.
7. a kind of preparation method of high-performance aromatic polyamides composite membrane according to claim 1, it is characterised in that the 3-
The chemical structure of two hydrocarbon amino propylamine is by shown in general formula (C):
The wherein R in the general formula (C)1And R2It is respectively selected from C1~C18Alkyl.
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| CN110038446A (en) * | 2019-05-31 | 2019-07-23 | 自然资源部天津海水淡化与综合利用研究所 | A kind of antipollution aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
| CN113230912A (en) * | 2021-04-29 | 2021-08-10 | 浙江理工大学 | Preparation method of chlorine-resistant composite nanofiltration membrane |
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