CN108997179A - Sulfur-bearing ether polyamine and its preparation method and application - Google Patents
Sulfur-bearing ether polyamine and its preparation method and application Download PDFInfo
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- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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Abstract
The present invention relates to a kind of sulfur-bearing ether polyamine and its preparation method and application and the anti-oxidant Sulfide-containing Hindered seperation films of a kind of chlorine-resistant and preparation method thereof, belong to polymeric material field.The present invention provides a kind of preparation method of sulfur-bearing ether polyamine, and the preparation method includes the following steps: the preparation of half aromatics polyhalo amide monomer;The purifying of half aromatics polyhalo amide monomer crude product;The preparation of Sulfide-containing Hindered polyamine monomers;The purifying of Sulfide-containing Hindered polyamine monomers solution.The present invention has synthesized a kind of polyamines containing high-content reduction group thioether (- S-) for the first time, and the reducible sulfur ether structure of high-content can be reacted with Active Chlorine, oxidisability chlorine of the consumption overwhelming majority in seperation film oxidation processes;More cross-linked structures are formed with acyl chlorides using multiple amidos in strand simultaneously, further promote the intensity of interfacial separation layer, so that significantly the service life of extension film, reduces the use cost of seperation film while keeping separation membrane separation efficiency and performance.
Description
Technical field
The present invention relates to a kind of sulfur-bearing ether polyamine and its preparation method and application and the anti-oxidant Sulfide-containing Hindereds of a kind of chlorine-resistant point
From film and preparation method thereof, belong to polymeric material field.
Background technique
UF membrane science is the separation new science research to emerge rapidly after the 1960s.UF membrane is due to simultaneous
Have the function of separation, concentration, purifying and purification, but have efficiently, energy-saving and environmental protection and filter process is simple, the features such as easily controllable,
The fields such as food, medicine, biology, the energy, water process, bionical are widely used at present, production, the life of the mankind are produced
Tremendous influence, it has also become one of most important means in current separation science.Seperation film is the core in membrane separating process, and
Membrane material is then the development foundation of seperation film.Due to its good separating effect, energy conservation and environmental protection wide using pH range the advantages that, fragrance
Polyamide composite film (TFC membrane) is since by invention in fields such as sea water desalination, municipal wastewater processing and pure water preparations
It is used widely, also becomes one of the research hotspot of material supply section scholar.
Biological pollution is the main reason for causing film properties to reduce, and according to statistics, at least 28% film failure is the life by film
Caused by object pollution.In order to reduce fouling membrane, it usually needs a certain amount of bacteria remover, such as hypochlorous acid are added in pending water
Sodium, chloramines, phosgene etc. are because its is cheap, significant effect is used widely.However, aromatic polyamides composite membrane once and this
The chlorination that amido bond will occur for the contact of class bacteria remover replaces, and irreversible phenyl ring chlorination and hydrolysis then occurs, causes compound
Membrane flux reduces, rejection reduces, and then loses separating property.In general, composite membrane is about 200- to the tolerance of Active Chlorine
Therefore 1000ppm*h in practical operation, needs the water inlet to composite membrane to carry out dechlorination processing, chlorine element contains in guarantee water inlet
Amount is lower than 1ppm, after separation, then carries out chlorination processing to treated water and is contaminated again in running water system to avoid it.
On the one hand continuous dechlorination, chlorination lead to complex process, on the other hand also increase cost.Therefore, a kind of fenestra knot is prepared
Structure is easy to control, separating property is excellent and the oxidation resistant seperation film film of chlorine-resistant will be it is very necessary, have it is very important basis reason
By and practical application value.
According to the oxidation mechanism of aromatic polyamides, membrane science men propose the chlorine-resistant that following scheme improves aromatic polyamides
Performance.(1) using the secondary amine in tertiary amine substituted amide group, the surface grafting (2) of such as N-H key based on amido bond is in amido bond
N-H between introduce aliphatic bridge, (3) are to introduce strong electron-withdrawing group group on the connected phenyl ring of N-H, (4) introduce in polymerization process or
Surface coating inorganic sheath keeps apart aramid layer and Active Chlorine.Although these method of modifying more or less improve multiple
Close the chlorine-resistant property of film, but generally also along with the flux decline of film, rejection decline, complex process and cost is raised asks
Topic.
So far, few as the anti-oxidant Sulfide-containing Hindered separation membrane material of chlorine-resistant and its in high activity chlorine seperation film field
Application report.
Summary of the invention
In view of the foregoing drawbacks, the present invention has synthesized one kind by the method for MOLECULE DESIGN for the first time and has contained high-content also former base
The polyamines of group thioether (- S-), and can be reacted with Active Chlorine using the reducible sulfur ether structure of high-content on its strand, consumption is exhausted
Most of oxidisability chlorine in seperation film oxidation processes;It is formed simultaneously using multiple amidos in strand with acyl chlorides more
Cross-linked structure further promotes the intensity of interfacial separation layer, thus while keeping it to separate membrane separation efficiency and performance,
The service life for significantly extending membrane module, reduces the operation and use cost of seperation film.
Technical solution of the present invention:
The invention solves first technical problem provide sulfur-bearing ether polyamine preparation method, the method includes as follows
Step:
The preparation of (1) half aromatics polyhalo amide monomer
By 103~232 parts of polyamines, 120~220 parts of alkali, 1~50 part of surfactant is added sequentially to 500~2000 parts
Deionized water in, dissolve much amine aqueous solutions at room temperature;By 522~696 parts of parachlorobenzoyl chloride or to fluorobenzoyl chloride
475.5~634 parts obtain mixed liquor with 600~5000 parts of organic solvents after mixing;Then the polyamines solution is added drop-wise to
In mixed liquor, after polyamines solution drips, it is thick to generate half aromatics polyhalo amide monomer by the reaction was continued at room temperature 2~12h
Product;
The purifying of (2) half aromatics polyhalo amide monomer crude products
Organic solvent in half aromatics polyhalo amide monomer crude product obtained by step (1) is steamed, is filtered, filter cake is collected,
Filter cake through deionized water wash remove water-solubility impurity, refilter, obtain white powder crude product, crude product through recrystallizing,
Colourless granules shape crystal is collected in filtering, and vacuum drying obtains half aromatics polyhalo amide monomer of purifying;
(3) preparation of Sulfide-containing Hindered polyamine monomers
Half 469~728 parts of aromatics polyhalo amide monomer prepared by step (2), 240~400 parts of p-aminophenyl thiophenol,
1000~3000 parts of polar solvent, 10~100 parts of dehydrating agent, in 140 DEG C~230 DEG C of temperature under 80~400 parts of stirrings of alkali
React 2~12 hours generation Sulfide-containing Hindered polyamine monomers solution;
(4) purifying of Sulfide-containing Hindered polyamine monomers solution
Sulfur-bearing ether polyamine solution obtained by step (3) is poured into and is allowed to precipitate in cold water, washs and filters through deionized water, is removed
Water-solubility impurity obtains sulfur-bearing ether polyamine after dry.
In the preparation method of sulfur-bearing ether polyamine, in step (1), polyamines is diethylenetriamine, triethylene tetramine, four ethylene five
Any one of amine or pentaethylene hexamine.
In the preparation method of sulfur-bearing ether polyamine, in step (1), the surfactant is sodium citrate, sodium laurate, heptan
Sodium saccharate, odium stearate, triethanolamine, lauryl sodium sulfate, dioctyl succinate disulfonate acid, sodium glycocholate, p-aminophenyl
Sodium sulfonate, tetrabutylammonium bromide, benzyltriethylammoinium chloride, dodecyltriethylammonium ammonium chloride, dodecyl dimethyl bromination
Any one of ammonium, 15- crown- 5,18- crown- 6, sodium alginate or fatty acid sorbitan.
In the preparation method of sulfur-bearing ether polyamine, in step (1) and step (4), the alkali be lithium hydroxide, sodium hydroxide,
Potassium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus or carbon
Any one of sour hydrogen barium.
In the preparation method of sulfur-bearing ether polyamine, in step (1), the organic solvent is methylene chloride, chloroform, four chlorinations
Any one of carbon, tetrachloroethanes, n-hexane, hexamethylene, normal octane, isooctane, petroleum ether or normal heptane.
In the preparation method of sulfur-bearing ether polyamine, in step (2), recrystallization solvent for use is water, methanol, ethyl alcohol, acetone, four
Hydrogen furans, formamide, acetamide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone and diformazan are sub-
At least one of sulfone.
In the preparation method of sulfur-bearing ether polyamine, in step (3), the polar solvent is N-Methyl pyrrolidone, N, N- bis-
Methylpropenyl urea, dimethyl sulfoxide, N, N, N ' N '-tetramethylurea, hexamethylphosphoramide, 2-Pyrrolidone, N- cyclohexyl
Pyrrolidones, dimethylformamide, 1,3- dimethyl-2-imidazolinone, dimethyl acetamide, quinoline, isoquinolin, sulfolane,
Any one of 2,4- dimethylsulfolane, N- methyl caprolactam.
In the preparation method of sulfur-bearing ether polyamine, in step (3), the dehydrating agent is toluene or dimethylbenzene.
Further, in step (4), the product after removing water-solubility impurity further removes impurity with ethanol washing.
The invention solves second technical problem a kind of sulfur-bearing ether polyamine is provided, the sulfur-bearing ether polyamine is using above-mentioned
Method is prepared.
Further, the sulfur-bearing ether polyamine is II compound represented of formula I or formula:
The invention solves third technical problem be to provide the application of above-mentioned sulfur-bearing ether polyamine, be used for preparing resistance to
The anti-oxidant Sulfide-containing Hindered seperation film of chlorine, method particularly includes: it is prepared using traditional interfacial polymerization, preparation including aqueous phase solution,
The preparation of organic phase solution and interface polymerization reaction, wherein the organic phase solution includes polynary acyl chlorides monomer and above-mentioned sulfur-bearing
Ether polyamine, the mass ratio of polynary acyl chlorides monomer and sulfur-bearing ether polyamine are as follows: polynary 0.1~5 parts by weight of acyl chlorides monomer, sulfur-bearing ether polyamine
0.1~10 parts by weight.
Further, the method that above-mentioned sulfur-bearing ether polyamine is used to prepare the anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant includes following step
It is rapid:
A), 10~100 parts by weight ultrafiltration membrane basement membranes are infiltrated at least 1~20min with 50~1000 parts by weight aqueous phase solutions
Afterwards, basement membrane must be infiltrated by removing the macroscopic aqueous phase solution of membrane surface;
B), the surface of the resulting infiltration basement membrane of step a) is infiltrated into 2~60s with 50~1000 parts by weight organic solution of acid chloride
After remove organic solution of acid chloride, then remove film surface unreacted monomer obtain composite membrane;
C), composite membrane obtained by step b) is placed in again in 0.1~1000 parts by weight organic sulfur-containing ether polyamine solution and reacts 20
Then~600s removes film surface unreacted polyamine monomers;
D), finally cleaned with deionized water and remove remaining impurity up to the anti-oxidant seperation film of chlorine-resistant.
Further, in the above method, in step a) aqueous phase solution using following methods prepare: weigh triethylamine and it is left-handed or
D-camphorsulfonic acid buffer solution, then weighs diamine monomer and is dissolved in buffer solution diamines aqueous phase solution is made;Diamines water phase
The concentration of diamine monomer is 1g/100ml~5g/100ml in solution;Wherein, the diamine monomer is p-phenylenediamine, isophthalic two
At least one of amine, butanediamine, hexamethylene diamine.
Further, in the above method, organic solution of acid chloride is prepared using following methods in step b): acyl chlorides is dissolved in solvent
In be prepared into organic phase solution of acid chloride, in organic phase solution of acid chloride the concentration of acyl chlorides be 0.1g/100ml~1g/100ml;Wherein,
Acyl chlorides is paraphthaloyl chloride, m-phthaloyl chloride, 1,3,5- pyromellitic trimethylsilyl chloride, 4,4 '-dimethyl chloride diphenyl sulfides
(TDC), bis- (4- formyl chloride diphenyl sulfide) benzene (2SC) or 1, at least one of 3- (4- formyl chloride diphenyl sulfide) benzene (m-2SC);It is molten
Agent is any one of hexamethylene, n-hexane, methylene chloride, chloroform, normal octane or isooctane.
Further, in the above method, organic sulfur-containing ether polyamine solution is prepared using following methods in step c): by Sulfide-containing Hindered
Polyamine monomers, which are dissolved in organic solvent, is made organic Sulfide-containing Hindered polyamines solution;Sulfur-bearing ether polyamine list in organic sulfur-containing ether polyamine solution
The concentration of body is 1g/100ml~5g/100ml;Wherein, organic solvent is ethyl alcohol, methanol, dimethylformamide, dimethylacetamide
At least one of amine, dimethyl sulfoxide, N-Methyl pyrrolidone;Sulfide-containing Hindered polyamine monomers polyamines Sulfide-containing Hindered described above is more
Amine monomers.
Further, the ultrafiltration membrane basement membrane is selected from ultrafiltration membrane made of following any materials: Kynoar (PVDF) gathers
Ethylene glycol terephthalate (PET), polybutylene terephthalate (PBT) (PBT), polycarbonate (PC), polyvinyl chloride (PVC),
Polyethylene (PE), polypropylene (PP), polysulfones (PSF), polyether sulfone (PES), polyether ethersulfone (PEES), polyphenylsulfone (PPSU),
Polyaryl thioether sulfone (PASS), polyamide (PA) or polyimides (PI).
The invention solves the 4th technical problem be to provide the preparation side of anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant a kind of
Method, the preparation method is that: it is prepared using traditional interfacial polymerization, the system of preparation, organic phase solution including aqueous phase solution
Standby and interface polymerization reaction, which is characterized in that the organic phase solution includes polynary acyl chlorides monomer and sulfur-bearing ether polyamine, polynary acyl
The mass ratio of chlorine monomer and sulfur-bearing ether polyamine are as follows: polynary 0.1~5 parts by weight of acyl chlorides monomer, 0.1~10 weight of sulfur-bearing ether polyamine
Part;Wherein, the sulfur-bearing ether polyamine is sulfur-bearing ether polyamine obtained above.The specific preparation method of seperation film is the same as in above-mentioned application
Preparation method.
The invention solves the 5th technical problem be a kind of anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant, the seperation film is adopted
It is made with preceding claim preparation method.
It in the present invention, is not particularly illustrated, the number of each raw material is parts by weight.
Beneficial effects of the present invention:
1. the present invention has synthesized the polyamines of a kind of high-content reduction group thioether (- S-) by the method for MOLECULE DESIGN,
And can be reacted with Active Chlorine using the reducible sulfur ether structure of high-content on its strand, the consumption overwhelming majority is aoxidized in seperation film
Oxidisability chlorine in treatment process;More cross-linked structures are formed with acyl chlorides using multiple amidos in strand simultaneously, are further mentioned
The intensity of interfacial separation layer is risen, so that it is used to prepare the anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant;In point for keeping its seperation film
While from efficiency and performance, significantly extends the service life of membrane module, reduce the operation and use cost of seperation film.
2. the anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant produced by the present invention has excellent chlorine-resistant property and mechanical performance, antibiosis
Object pollutant performance is excellent, can be used as preparation high-performance separation membrane material, is with a wide range of applications.
3. the preparation process of seperation film is prepared using traditional interfacial polymerization in the present invention, modified etc. compared to existing surface
Its preparation process flow of method is easy, easy to operate, easy to control, not high to equipment requirement.
4. the water flux and rejection of gained seperation film of the invention are suitable with traditional polymerizing polyamide film, even more preferably, phase
For traditional seperation film, its service life significantly extends, but its efficiency and performance are still kept well.
Detailed description of the invention
Fig. 1 be embodiment 1,2 gained Sulfide-containing Hindered triamines, Sulfide-containing Hindered tetramine infrared spectrum.
Fig. 2 is the nuclear magnetic spectrogram of 1 gained Sulfide-containing Hindered triamine of embodiment.
Fig. 3 is the nuclear magnetic spectrogram of 2 gained Sulfide-containing Hindered tetramine of embodiment.
Fig. 4 is without (the original 0-TA- before seperation film (comparative example 1) chlorination by the grafting of thioether polyamines
TFC membrane) and chlorination after (the chlorinated 0-TA-TFC membrane) infared spectrum comparison.
Fig. 5 is (the original 1%-TA- before seperation film (embodiment 1) chlorination being grafted by 1% thioether polyamines
TFC membrane) and chlorination after (the chlorinated 1%-TA-TFC membrane) infared spectrum comparison.
Fig. 6 is (the original 3%-TA- before seperation film (embodiment 3) chlorination being grafted by 3% thioether polyamines
TFC membrane) and chlorination after (the chlorinated 3%-TA-TFC membrane) infared spectrum comparison.
Fig. 7, which is comparative example 1, --- without the seperation film (TFC-TA-0) of thioether polyamines grafting, embodiment 1 --- to be passed through
The seperation film (TFC-TA-1%) and embodiment 3 of 1% thioether polyamines --- the seperation film (TFC- being grafted by 3% thioether polyamines
TA-3%) water flux and the variation diagram of rejection after chlorination.
Specific embodiment
Following steps can be used in the preparation method of sulfur-bearing ether polyamine provided by the invention:
The preparation of (1) half aromatics polyhalo amide monomer
By 103~232 parts of polyamines, 120~220 parts of alkali, 1~50 part of surfactant is added sequentially to 500~2000 parts
Deionized water in, dissolve at room temperature;By 522~696 parts of parachlorobenzoyl chloride or to 475.5~634 parts of fluorobenzoyl chloride
It is added in three-neck flask with 600~5000 parts of organic solvents, then drips above-mentioned configured polyamines solution after mixing
It is added in above-mentioned three-neck flask, after polyamines solution drips, the reaction was continued at room temperature 2~12h, half aromatics polyhalo of generation
Amide monomer;
The purifying of (2) half aromatics polyhalo amide monomers
Organic solvent in above-mentioned half aromatics polyhalo amide is steamed, is filtered, filter cake is collected, filter cake is washed through deionization
It washs three times, removes water-solubility impurity, refilter, obtain white powder crude product, crude product is recrystallized, and is filtered, is collected nothing
Coloured particles shape crystal, vacuum drying, obtains half aromatics polyhalo amide monomer of purifying, structural formula is as follows:
Wherein: X=F or Cl;
(3) preparation of Sulfide-containing Hindered polyamine monomers
By half 469~728 parts of aromatics polyhalo amide monomer of above-mentioned preparation, 240~400 parts of p-aminophenyl thiophenol, pole
1000~3000 parts of solvent of property, 10~100 parts of dehydrating agent, 80~400 parts of alkali sequentially add with blender, thermometer and reflux
In the three-necked bottle of condenser, in 140 DEG C~230 DEG C of temperature reactions, 2~12 hours generation Sulfide-containing Hindered polyamine monomers;
(4) purifying of Sulfide-containing Hindered polyamine monomers
Above-mentioned sulfur-bearing ether polyamine solution is poured into and is allowed to precipitate in cold water, washs and filters through deionized water, is removed water-soluble
Impurity, product further remove impurity with ethanol washing, obtain Sulfide-containing Hindered polyamine monomers after dry, structural formula is as follows:
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made according to the content of aforementioned present invention.
Embodiment 1
One, the preparation of Sulfide-containing Hindered Triamine monomer, includes the following steps:
The preparation of three chloro amide monomer of (1) half aromatics
By diethylenetriamine 103g, NaOH 120g, sodium citrate 1g is added sequentially in the deionized water of 500ml, in room
The lower dissolution of temperature obtains polyamines solution;Parachlorobenzoyl chloride 522g and 600ml methylene chloride are added to three necks after mixing to burn
In bottle, then above-mentioned configured polyamines solution is added drop-wise in above-mentioned three-neck flask, after polyamines solution drips, in room temperature
Lower the reaction was continued 12h, generates half aromatics, three chloro amide monomer;
The purifying of three chloro amide monomer of (2) half aromatics
Organic solvent in above-mentioned half aromatics, three chloroamides is steamed, is filtered, filter cake is collected, filter cake is washed through deionization
It washs three times, removes water-solubility impurity, refilter, obtain white powder crude product, crude product is recrystallized, and is filtered, is collected nothing
Coloured particles shape crystal, vacuum drying, obtains half aromatics, the three chloro amide monomer of purifying;
(3) preparation of Sulfide-containing Hindered polyamine monomers
By the half aromatics three chloro amide monomer 517g of above-mentioned preparation, p-aminophenyl thiophenol 240g, N-Methyl pyrrolidone
1000ml, toluene 10g, lithium hydroxide 80g are sequentially added in the three-necked bottle with blender, thermometer and reflux condenser, in
140 DEG C of temperature reactions, 12 hours generation Sulfide-containing Hindered Triamine monomers;
(4) purifying of Sulfide-containing Hindered Triamine monomer
Above-mentioned Sulfide-containing Hindered triamine solution is poured into and is allowed to precipitate in cold water, washs and filters through deionized water, is removed water-soluble
Impurity, product further remove impurity with ethanol washing, obtain Sulfide-containing Hindered Triamine monomer, infrared, nuclear-magnetism structure after dry
Characterization is as shown in Figure 1, 2 respectively;
Two, the preparation of organic phase solution and aqueous phase solution:
1) preparation of organic solution of acid chloride:
1,3,5- pyromellitic trimethylsilyl chloride of 0.1g is weighed according to predetermined ratio, and is dissolved in the hexamethylene of 100ml and being prepared into
Machine phase solution -1,3,5- pyromellitic trimethylsilyl chloride solution, the concentration of acyl chlorides is 0.1% (w/v) in organic phase solution;Solution is close
Envelope saves, for use;
2) preparation of two amine aqueous solutions:
Triethylamine and left or right rotation camphorsulfonic acid buffer solution 100ml are measured, the m-phenylene diamine (MPD) monomer of 1g is then weighed
It is dissolved in the buffer solution of preparation and homogeneous phase solution is made --- m-phenylene diamine (MPD) aqueous solution, m-phenylene diamine (MPD) list in m-phenylene diamine (MPD) aqueous solution
The concentration of body is 1% (w/v);And be sealed, for use;
3) preparation of organic phase sulfur-bearing ether polyamine solution:
The Sulfide-containing Hindered Triamine monomer for weighing 1g is dissolved in the ethyl alcohol of 100ml/dimethylformamide in the mixed solvent (ethyl alcohol and two
The volume ratio of methylformamide be 1:1) in be made into organic phase sulfur-bearing ether polyamine solution-triamine solution, Sulfide-containing Hindered in triamine solution
The concentration of Triamine monomer is 1% (w/v);It is sealed, it is spare;
Three, interfacial polymerization prepares the anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant:
A), after 10g polyvinylidene fluoride (PVDF) ultrafiltration membrane basement membrane being infiltrated 1min with the 100g m-phenylene diamine (MPD) aqueous solution of configuration, remove
The macroscopic m-phenylene diamine (MPD) aqueous solution of membrane surface;
B), 1,3,5- pyromellitic trimethylsilyl chloride solution crosses m-phenylene diamine (MPD) solution immersion prepared by 50g basement membrane
Organic phase solution is removed after surface infiltration 10s, and with cyclohexane 2 times to remove film surface unreacted monomer, obtained initially multiple
Close film;
C), according to specific requirement, treated initial composite film is placed in again in 200g triamine solution and reacts 60s,
6 times are cleaned except striping with ethyl alcohol/dimethylformamide mixed solvent (volume ratio of ethyl alcohol and dimethylformamide is 1:1) again
The unreacted Triamine monomer in surface, obtains composite membrane;
D), composite membrane obtained above is cleaned 3 times with deionized water and obtains seperation film to remove remaining impurity, then will
Film is stored in 2 DEG C of deionized water, spare;
After obtained seperation film is used for chlorine-resistant experiment (through 200ppm liquor natrii hypochloritis immersion treatment), before chlorination
(the chlorinated 1%-TA-TFC after (the original 1%-TA-TFC membrane) and chlorination
Membrane infared spectrum variation) is as shown in Figure 5 respectively.
In addition, the present invention also carries out chlorine-resistant experiment to the seperation film (comparative example 1) of no grafting thioether polyamines, before chlorination
After (the original 0-TA-TFC membrane) and chlorination (the chlorinated 0-TA-TFC membrane)
Infared spectrum is as shown in Figure 4.Infared spectrum (figure before and after the chlorination of separation membrane sample relative to no grafting thioether polyamines
4) it, can be clearly observed, being grafted before and after the separation membrane sample chlorination of thioether polyamines in 1640cm in Fig. 5-1The N-H at place inhales
Receipts have almost no change, and do not have the separation membrane sample for being grafted thioether polyamines in Fig. 4 after chlorination, in 1640cm-1The N-H at place
Absorption peak strength is obviously weaker than before chlorination, shows that the N-H of amido bond is replaced by Cl.
In addition, the present invention is also tested for after the seperation film chlorination for not being grafted thioether polyamines and 1 gained seperation film of embodiment
The flux and rejection of sample after chlorination, as a result as shown in Figure 7;As shown in Figure 7, after embodiment 1 (TA-TFC-1%) chlorination
The water flux and rejection of seperation film, relative to the sample (TA- not after the blank seperation film chlorination of thioether polyamines grafting
TFC-0 flux) is obviously big, and rejection is then maintained at level of approximation.
Embodiment 2
One, the preparation of Sulfide-containing Hindered tetramine monomers, includes the following steps:
The preparation of four fluoro amide monomer of (1) half aromatics
By triethylene tetramine 174g, NaOH 220g, dioctyl succinate disulfonate acid 10g is added sequentially to going for 1000ml
In ionized water, dissolve at room temperature;Three necks will be added to after mixing to fluorobenzoyl chloride 634g and 2000ml n-hexane to burn
In bottle, then above-mentioned configured polyamines solution is added drop-wise in above-mentioned three-neck flask, after polyamines solution drips, in room temperature
Lower the reaction was continued 2h, generates half aromatics, four fluoro amide monomer;
The purifying of four fluoro amide monomer of (2) half aromatics
Organic solvent in above-mentioned half aromatics, four fluoro amide is steamed, is filtered, filter cake is collected, filter cake is washed through deionization
It washs three times, removes water-solubility impurity, refilter, obtain white powder crude product, crude product is recrystallized, and is filtered, is collected nothing
Coloured particles shape crystal, vacuum drying, obtains half aromatics, the four fluoro amide monomer of purifying;
(3) preparation of Sulfide-containing Hindered tetramine monomers
By the half aromatics four fluoro amide monomer 662g of above-mentioned preparation, p-aminophenyl thiophenol 400g, dimethyl sulfoxide
2500ml, dimethylbenzene 20g, sodium hydroxide 280g are sequentially added in the three-necked bottle with blender, thermometer and reflux condenser,
In 160 DEG C of temperature reactions, 8 hours generation Sulfide-containing Hindered tetramine monomers;
(4) purifying of Sulfide-containing Hindered tetramine monomers
Above-mentioned four amine aqueous solution of Sulfide-containing Hindered is poured into and is allowed to precipitate in cold water, washs and filters through deionized water, is removed water-soluble
Impurity, product further remove impurity with ethanol washing, obtain Sulfide-containing Hindered tetramine monomers, infrared, nuclear-magnetism structure after dry
Characterization is as shown in Figure 1,3 respectively;
Two, the preparation of organic phase solution and aqueous phase solution:
1) preparation of organic solution of acid chloride:
0.1g 1,3,5- pyromellitic trimethylsilyl chloride, 0.1g 4,4 '-dimethyl chloride diphenyl sulfide are weighed according to predetermined ratio
(TDC), it and is dissolved in the n-hexane of 100ml and is prepared into organic solution of acid chloride, the concentration of acyl chlorides is 0.2% in organic phase solution
(w/v);Solution is sealed, for use;
2) preparation of two amine aqueous solutions:
Triethylamine and left or right rotation camphorsulfonic acid buffer solution 100ml are measured, the p-phenylenediamine monomer of 2g is then weighed
It is dissolved in the buffer solution of preparation and p-phenylenediamine aqueous solution is made, the concentration of diamine monomer is 2% (w/v) in two amine aqueous solutions;
And be sealed, for use;
3) preparation of organic phase sulfur-bearing ether polyamine solution:
The Sulfide-containing Hindered tetramine monomers for weighing 2g are dissolved in the methanol of 100ml/dimethyl acetamide mixed solvent (methanol and diformazan
Yl acetamide volume ratio 1:1) in be made into homogeneous phase solution 2% (w/v), be sealed, it is spare;
Three, interfacial polymerization prepares the anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant:
A), after 20g polysulfone ultrafiltration membrane basement membrane being infiltrated 2min with the 300g p-phenylenediamine aqueous solution of configuration, basement membrane table is removed
Macroscopic two amine aqueous solution in face;
B), the upper surface for the basement membrane for being crossed m-phenylene diamine (MPD) solution immersion with the organic phase solution of acid chloride of prepared 150g
Organic phase solution is removed after infiltration 2s, and cleans 6 times with n-hexane to remove film surface unreacted monomer;
C), according to specific requirement, by treated composite membrane again as reacting 20s in tetra- amine aqueous solution of 100g, then use
Methanol/dimethyl acetamide mixed solvent (methanol and dimethyl acetamide volume ratio 1:1) clean 2 times it is not anti-to remove film surface
Answer tetramine monomers;
D), composite membrane obtained above is cleaned 3 times with deionized water to remove remaining impurity, is then stored in film
It is spare in 2 DEG C of deionized water.
Embodiment 3
One, the preparation of thioether Triamine monomer, includes the following steps:
The preparation of three fluoro amide monomer of (1) half aromatics
By diethylenetriamine 103g, NaOH 150g, tetrabutylammonium bromide 25g is added sequentially to the deionized water of 2500ml
In, it dissolves at room temperature;Fluorobenzoyl chloride 475.5g and 2100ml chloroform will be added in three-neck flask after mixing, so
Above-mentioned configured polyamines solution is added drop-wise in above-mentioned three-neck flask afterwards, after polyamines solution drips, is continued at room temperature
8h is reacted, half aromatics, three fluoro amide monomer is generated;
The purifying of three fluoro amide monomer of (2) half aromatics
Organic solvent in above-mentioned half aromatics, three fluoro amide is steamed, is filtered, filter cake is collected, filter cake is washed through deionization
It washs three times, removes water-solubility impurity, refilter, obtain white powder crude product, crude product is recrystallized, and is filtered, is collected nothing
Coloured particles shape crystal, vacuum drying, obtains half aromatics, the three fluoro amide monomer of purifying;
(3) preparation of Sulfide-containing Hindered Triamine monomer
By the half aromatics three fluoro amide monomer 469g of above-mentioned preparation, p-aminophenyl thiophenol 280g, dimethylformamide
1800ml, toluene 55g, potassium carbonate 400g are sequentially added in the three-necked bottle with blender, thermometer and reflux condenser, Yu Wen
Spend 150 DEG C of reactions, 11 hours generation Sulfide-containing Hindered Triamine monomers;
(4) purifying of Sulfide-containing Hindered Triamine monomer
Above-mentioned Sulfide-containing Hindered triamine solution is poured into and is allowed to precipitate in cold water, washs and filters through deionized water, is removed water-soluble
Impurity, product further remove impurity with ethanol washing, obtain Sulfide-containing Hindered Triamine monomer after dry;
Two, the preparation of organic phase solution and aqueous phase solution:
1) preparation of organic solution of acid chloride:
0.1g m-phthaloyl chloride, 0.2g 1,3- (4- formyl chloride diphenyl sulfide) benzene are weighed according to predetermined ratio, and is dissolved in
Homogeneous phase solution is prepared into the normal octane of 100ml, the concentration of acyl chlorides is 0.3% (w/v) in organic phase solution;Solution is sealed and is protected
It deposits, for use;
2) preparation of two amine aqueous solutions:
Triethylamine and left or right rotation camphorsulfonic acid buffer solution 100ml are measured, m-phenylene diamine (MPD) monomer is then weighed and is dissolved in
Two amine aqueous solutions are made in the buffer solution of preparation, the concentration of diamine monomer is 2% (w/v) in two amine aqueous solutions;And seal guarantor
It deposits, for use;
3) preparation of organic phase sulfur-bearing ether polyamine solution:
The Sulfide-containing Hindered Triamine monomer for weighing 3g is dissolved in the ethyl alcohol of 100ml/dimethyl sulfoxide mixed solvent (ethyl alcohol and dimethyl sulfoxide
Volume ratio be 1:1) in be made into Sulfide-containing Hindered Triamine monomer concentration be 3% (w/v) homogeneous phase solution, be sealed, it is spare;
Three, interfacial polymerization prepares the anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant:
A), after 10g polyamide ultrafiltration membrane basement membrane being infiltrated 3min with the 500g m-phenylene diamine (MPD) aqueous solution of configuration, basement membrane is removed
Macroscopic two amine aqueous solution in surface;
B), the upper surface infiltration for the basement membrane for being crossed m-phenylene diamine (MPD) solution immersion with the solution of acid chloride of prepared 1000g
Organic phase solution is removed after 30s, and with cyclohexane 4 times to remove film surface unreacted monomer;
C), according to specific requirement, by treated composite membrane again as reacting 30s in 800g triamine solution, then use
Ethyl alcohol/dimethyl sulfoxide mixed solvent (volume ratio of ethyl alcohol and dimethyl sulfoxide is 1:1) cleaning 5 times to remove film surface unreacted three
Amine monomers;
D), composite membrane obtained above is cleaned 3 times with deionized water to remove remaining impurity, is then stored in film
It is spare in 5 DEG C of deionized water;
After obtained seperation film is used for chlorine-resistant experiment (through 200ppm liquor natrii hypochloritis immersion treatment), before chlorination
(the chlorinated 3%-TA-TFC after (the original 3%-TA-TFC membrane) and chlorination
Membrane infared spectrum variation) is as shown in fig. 6, relative to no separation membrane sample (comparative example 1) for being grafted thioether polyamines
Chlorination before and after infared spectrum (Fig. 4), can be clearly observed, be grafted in Fig. 6 thioether polyamines separation membrane sample chlorination
Front and back is in 1640cm-1The N-H absorption at place has almost no change, and does not have the separation membrane sample for being grafted thioether polyamines through chlorine in Fig. 4
After change, in 1640cm-1The N-H absorption peak strength at place is obviously weaker than before chlorination, shows that the N-H of amido bond is replaced by Cl.
In addition, the present invention is also tested for after seperation film (comparative example 1) chlorination for not being grafted thioether polyamines and 3 institute of embodiment
The flux and rejection of sample after obtaining seperation film chlorination, as a result as shown in Figure 7;As shown in Figure 7,3 (TA-TFC- of embodiment
3%) after chlorination seperation film water flux and rejection, relative to not by thioether polyamines grafting blank seperation film chlorination after
Sample (TA-TFC-0) flux it is obviously big, and rejection is then maintained at level of approximation.
Embodiment 4
One, the preparation of Sulfide-containing Hindered tetramine monomers, includes the following steps:
The preparation of four chloro amide monomer of (1) half aromatics
Triethylene tetramine 174g, 6 35g of NaOH 180g, 18- crown- are added sequentially in the deionized water of 3500ml, in
It dissolves at room temperature;Parachlorobenzoyl chloride 696g and 4200ml hexamethylene are added in three-neck flask after mixing, then will
Above-mentioned configured polyamines solution is added drop-wise in above-mentioned three-neck flask, and after polyamines solution drips, the reaction was continued at room temperature
8h generates half aromatics, four chloro amide monomer;
The purifying of four chloro amide monomer of (2) half aromatics
Organic solvent in above-mentioned half aromatics, four chloroamides is steamed, is filtered, filter cake is collected, filter cake is washed through deionization
It washs three times, removes water-solubility impurity, refilter, obtain white powder crude product, crude product is recrystallized, and is filtered, is collected nothing
Coloured particles shape crystal, vacuum drying, obtains half aromatics, the four chloro amide monomer of purifying;
(3) preparation of Sulfide-containing Hindered tetramine monomers
By the half aromatics four chloro amide monomer 726g of above-mentioned preparation, p-aminophenyl thiophenol 360g, dimethyl acetamide
2500ml, toluene 80g, barium hydroxide 320g are sequentially added in the three-necked bottle with blender, thermometer and reflux condenser, in
160 DEG C of temperature reactions, 8 hours generation Sulfide-containing Hindered tetramine monomers;
(4) purifying of Sulfide-containing Hindered tetramine monomers
Above-mentioned four amine aqueous solution of Sulfide-containing Hindered is poured into and is allowed to precipitate in cold water, washs and filters through deionized water, is removed water-soluble
Impurity, product further remove impurity with ethanol washing, obtain Sulfide-containing Hindered tetramine monomers after dry;
Two, the preparation of organic phase solution and aqueous phase solution:
1) preparation of organic solution of acid chloride:
4,4 '-dimethyl chloride diphenyl sulfide of 0.5g is weighed according to predetermined ratio, and is dissolved in the chloroform of 100ml and being prepared into
Organic phase solution of acid chloride, the concentration of acyl chlorides is 0.5% (w/v) in organic phase solution of acid chloride;Solution is sealed, for use;
2) preparation of two amine aqueous solutions:
It measures triethylamine and left or right rotation camphorsulfonic acid buffer solution 100ml, the hexamethylene diamine monomer for then weighing 3g is molten
Two amine aqueous solutions are made in the buffer solution of preparation, the concentration of diamine monomer is 3% (w/v) in two amine aqueous solutions;And it seals
It saves, for use;
3) preparation of organic phase sulfur-bearing ether polyamine solution:
The Sulfide-containing Hindered tetramine monomers for weighing 5g are dissolved in the methanol of 100ml/dimethyl sulfoxide mixed solvent (methanol and dimethyl sulfoxide
Volume ratio be 1:1) in be made into concentration be 5% (w/v) homogeneous phase solution, be sealed, it is spare;
Three, interfacial polymerization prepares the anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant:
A), 10g polyethylene terephthalate ultrafiltration membrane basement membrane is infiltrated with the 600g hexamethylene diamine aqueous solution of configuration
After 3min, macroscopic two amine aqueous solution of membrane surface is removed;
B), after the upper surface infiltration 40s for the basement membrane for being crossed hexamethylene diamine solution immersion with prepared 800g solution of acid chloride
Organic phase solution is removed, and cleans 4 times with chloroform to remove film surface unreacted monomer;
C), according to specific requirement, by treated composite membrane again as reacting 20s in tetra- amine aqueous solution of 600g, then use
Methanol/dimethyl sulfoxide mixed solvent (volume ratio of methanol and dimethyl sulfoxide is 1:1) cleaning 4 times to remove film surface unreacted four
Amine monomers;
D), composite membrane obtained above is cleaned 3 times with deionized water to remove remaining impurity, is then stored in film
It is spare in 5 DEG C of deionized water.
Claims (10)
1. the preparation method of sulfur-bearing ether polyamine, which is characterized in that the preparation method includes the following steps:
The preparation of (1) half aromatics polyhalo amide monomer
By 103~232 parts of polyamines, 120~220 parts of alkali, 1~50 part of surfactant is added sequentially to 500~2000 parts and goes
In ionized water, much amine aqueous solutions are dissolved at room temperature;By 522~696 parts of parachlorobenzoyl chloride or to fluorobenzoyl chloride 475.5~
634 parts obtain mixed liquor with 600~5000 parts of organic solvents after mixing;Then the polyamines solution is added drop-wise to mixed liquor
In, after polyamines solution drips, the reaction was continued at room temperature 2~12h generates half aromatics polyhalo amide monomer crude product;
The purifying of (2) half aromatics polyhalo amide monomer crude products
Organic solvent in half aromatics polyhalo amide monomer crude product obtained by step (1) is steamed, is filtered, filter cake, filter cake are collected
It is washed through deionized water and removes water-solubility impurity, refiltered, obtain white powder crude product, crude product is recrystallized, filtering,
Colourless granules shape crystal is collected, vacuum drying obtains half aromatics polyhalo amide monomer of purifying;
(3) preparation of Sulfide-containing Hindered polyamine monomers
Half 469~728 parts of aromatics polyhalo amide monomer prepared by step (2), 240~400 parts of p-aminophenyl thiophenol, polarity
1000~3000 parts of solvent, 10~100 parts of dehydrating agent, 2 are reacted in 140 DEG C~230 DEG C of temperature under 80~400 parts of stirrings of alkali
~12 hours generation Sulfide-containing Hindered polyamine monomers solution;
(4) purifying of Sulfide-containing Hindered polyamine monomers solution
Sulfur-bearing ether polyamine solution obtained by step (3) is poured into and is allowed to precipitate in cold water, washs and filters through deionized water, is removed water-soluble
Property impurity, obtain sulfur-bearing ether polyamine after dry.
2. the preparation method of sulfur-bearing ether polyamine according to claim 1, which is characterized in that in step (1), polyamines is diethyl
Any one of alkene triamine, triethylene tetramine, tetraethylenepentamine or pentaethylene hexamine;Or:
In step (1), the surfactant is sodium citrate, sodium laurate, heptose sodium sugar, odium stearate, triethanolamine, ten
Sodium dialkyl sulfate, dioctyl succinate disulfonate acid, sodium glycocholate, sodium sulfanilate, tetrabutylammonium bromide, three second of benzyl
Ammonium chloride, dodecyltriethylammonium ammonium chloride, Dodecydimethylammonium bronides, 15- crown- 5,18- crown- 6, sodium alginate or
Any one of fatty acid sorbitan;Or:
In step (1) and step (4), the alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, lithium carbonate, carbon
Any one of sour sodium, potassium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus or barium bicarbonate;Or:
In step (1), the organic solvent is methylene chloride, chloroform, carbon tetrachloride, tetrachloroethanes, n-hexane, hexamethylene, just
Any one of octane, isooctane, petroleum ether or normal heptane.
3. the preparation method of sulfur-bearing ether polyamine according to claim 1 or 2, which is characterized in that in step (2), recrystallization
Solvent for use is water, methanol, ethyl alcohol, acetone, tetrahydrofuran, formamide, acetamide, N,N-dimethylformamide, N, N- diformazan
At least one of yl acetamide, N-Methyl pyrrolidone and dimethyl sulfoxide;Or:
In step (3), the polar solvent be N-Methyl pyrrolidone, N, N- dimethyl propylene alkenyl urea, dimethyl sulfoxide, N, N,
N ' N '-tetramethylurea, hexamethylphosphoramide, 2-Pyrrolidone, N- cyclohexyl pyrrolidone, dimethylformamide, 1,3- bis-
Methyl -2- imidazolone, dimethyl acetamide, quinoline, isoquinolin, sulfolane, 2,4- dimethylsulfolane or N- methyl are in oneself
Any one of amide;Or:
In step (3), the dehydrating agent is toluene or dimethylbenzene.
4. a kind of sulfur-bearing ether polyamine, which is characterized in that the sulfur-bearing ether polyamine uses the described in any item sides of claims 1 to 3
Method is prepared.
5. a kind of sulfur-bearing ether polyamine according to claim 4, which is characterized in that the sulfur-bearing ether polyamine is formula I or formula II
Compound represented:
6. the application of sulfur-bearing ether polyamine, which is characterized in that the sulfur-bearing ether polyamine is used to prepare the anti-oxidant Sulfide-containing Hindered separation of chlorine-resistant
Film, the preparation method comprises the following steps: prepared using traditional interfacial polymerization, the preparation of preparation, organic phase solution including aqueous phase solution and
Interface polymerization reaction, wherein the organic phase solution includes polynary acyl chlorides monomer and the sulfur-bearing ether polyamine, polynary acyl chlorides monomer
With the mass ratio of sulfur-bearing ether polyamine are as follows: polynary 0.1~5 parts by weight of acyl chlorides monomer, 0.1~10 parts by weight of sulfur-bearing ether polyamine;It is described
Sulfur-bearing ether polyamine is sulfur-bearing ether polyamine described in claim 4 or 5, or uses the described in any item methods of claims 1 to 3
It is prepared.
7. the application of sulfur-bearing ether polyamine according to claim 6, which is characterized in that the sulfur-bearing ether polyamine is used to prepare resistance to
The method of the anti-oxidant Sulfide-containing Hindered seperation film of chlorine includes the following steps:
A), after 10~100 parts by weight ultrafiltration membrane basement membranes being infiltrated at least 1~20min with 50~1000 parts by weight aqueous phase solutions, remove
Go the macroscopic aqueous phase solution of membrane surface that must infiltrate basement membrane;
B), removed after the surface of the resulting infiltration basement membrane of step a) being infiltrated 2~60s with 50~1000 parts by weight organic solution of acid chloride
Organic solution of acid chloride is gone, film surface unreacted monomer is then removed and obtains composite membrane;
C), by composite membrane obtained by step b) be placed in again reaction 20 in 0.1~1000 parts by weight organic sulfur-containing ether polyamine solution~
Then 600s removes film surface unreacted polyamine monomers;
D), finally cleaned with deionized water and remove remaining impurity up to the anti-oxidant seperation film of chlorine-resistant.
8. the application of sulfur-bearing ether polyamine according to claim 7, which is characterized in that
Aqueous phase solution is prepared using following methods in step a): triethylamine and left or right rotation camphorsulfonic acid buffer solution are weighed,
Then it weighs diamine monomer and is dissolved in buffer solution and diamines aqueous phase solution is made;The concentration of diamine monomer is in diamines aqueous phase solution
1g/100ml~5g/100ml;Wherein, the diamine monomer be p-phenylenediamine, m-phenylene diamine (MPD), butanediamine, in hexamethylene diamine at least
It is a kind of;Or:
Organic solution of acid chloride is prepared using following methods in step b): acyl chlorides is dissolved in solvent to be prepared into organic phase acyl chlorides molten
Liquid, the concentration of acyl chlorides is 0.1g/100ml~1g/100ml in organic phase solution of acid chloride;Wherein, acyl chlorides be paraphthaloyl chloride,
M-phthaloyl chloride, 1,3,5- pyromellitic trimethylsilyl chloride, 4,4 '-dimethyl chloride diphenyl sulfides, bis- (4- formyl chloride diphenyl sulfide) benzene or
At least one of 1,3- (4- formyl chloride diphenyl sulfide) benzene;Solvent be hexamethylene, n-hexane, methylene chloride, chloroform, normal octane or
Any one of isooctane;Or:
Organic sulfur-containing ether polyamine solution is prepared using following methods in step c): Sulfide-containing Hindered polyamine monomers are dissolved in organic solvent
Organic Sulfide-containing Hindered polyamines solution is made;In organic sulfur-containing ether polyamine solution the concentration of Sulfide-containing Hindered polyamine monomers be 1g/100ml~
5g/100ml;Wherein, organic solvent is ethyl alcohol, methanol, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, N- methyl
At least one of pyrrolidones;Sulfide-containing Hindered polyamine monomers polyamines Sulfide-containing Hindered polyamine monomers described above;Or:
In step a), the ultrafiltration membrane basement membrane is selected from ultrafiltration membrane made of following any materials: Kynoar, poly- terephthaldehyde
Sour glycol ester, polybutylene terephthalate (PBT), polycarbonate, polyvinyl chloride, polyethylene, polypropylene, polysulfones, polyether sulfone,
Polyether ethersulfone, polyphenylsulfone, polyaryl thioether sulfone, polyamide or polyimides.
9. the preparation method of the anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant, the preparation method is that: use traditional interfacial polymerization legal system
It is standby, the preparation of preparation, organic phase solution including aqueous phase solution and interface polymerization reaction, which is characterized in that described organic to mix
Liquid includes polynary acyl chlorides monomer and sulfur-bearing ether polyamine, the mass ratio of polynary acyl chlorides monomer and sulfur-bearing ether polyamine are as follows: polynary acyl chlorides list
0.1~5 parts by weight of body, 0.1~10 parts by weight of sulfur-bearing ether polyamine;Wherein, the sulfur-bearing ether polyamine is described in claim 4 or 5
Sulfur-bearing ether polyamine, or be prepared using the described in any item methods of claims 1 to 3.
10. a kind of anti-oxidant Sulfide-containing Hindered seperation film of chlorine-resistant, which is characterized in that the seperation film uses system as claimed in claim 9
Preparation Method is made.
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CN114907828A (en) * | 2021-02-08 | 2022-08-16 | 中国石油化工股份有限公司 | Green and environment-friendly composition with sulfur dissolving function and preparation method and application thereof |
CN114907828B (en) * | 2021-02-08 | 2024-02-09 | 中国石油化工股份有限公司 | Environment-friendly composition with sulfur dissolving function and preparation method and application thereof |
CN113416336A (en) * | 2021-06-11 | 2021-09-21 | 四川大学 | Fluorine-containing end group active hydroxyl friction-resistant high-shear-resistant composite rubber material |
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