CN108201793A - A kind of preparation method of aromatic polymer anti-soil film - Google Patents
A kind of preparation method of aromatic polymer anti-soil film Download PDFInfo
- Publication number
- CN108201793A CN108201793A CN201710341072.6A CN201710341072A CN108201793A CN 108201793 A CN108201793 A CN 108201793A CN 201710341072 A CN201710341072 A CN 201710341072A CN 108201793 A CN108201793 A CN 108201793A
- Authority
- CN
- China
- Prior art keywords
- polymer
- reaction
- film
- preparation
- aromatic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2381/06—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a kind of preparation methods of aromatic polymer anti-soil film.This method is realized in water phase using phase transfer catalysis (PTC) introduces halogen methyl in polymer surfaces, and the fragrant membrane material surface of method modification of antipollution group is further grafted by atom transferred free radical living polymerization.Halomethylation reaction of the present invention occurs over just film surface, reagent consumption is greatly reduced, the problems such as tradition is avoided to carry out the reaction of halomethylation to polymer body using organic solvent, is not related to organic solvent recycling, therefore reduce cost, reduce the probability of environmental pollution；Phase transfer catalyst is environmental-friendly stabilization organic compound, can be recycled, better than tradition to water sensitive, it is difficult to the SnCl recycled4Wait lewis acid catalysts.The present invention can carry out halomethylation and graft polymerization to the surface of any polymer for having an aromatic structure, have wide applicability, be suitable for industrializing.
Description
Technical field
The invention belongs to high-molecular organic material fields, and in particular to a kind of preparation method of aromatic polymer anti-soil film.
Background technology
Fragrant macromolecule polymer material is a kind of heat-resisting, stable mechanical performance high-performance polymer, water process,
The fields such as food industry, medical medical treatment, desalination have a wide range of applications.Such as aromatic polysulfones class, polyamide-based membrane material can divide
Not Yong Yu the ultrafiltration membrane of water process, NF membrane, reverse osmosis membrane and forward osmosis membrane preparation.Functionalization base is introduced by film surface
Group, then grafting have antifouling hydrophilic polymer material, can effectively reduce membrane pollution problem, improve the performance of film and using effect
Rate.For medical instrument, more than 30% postoperative infection is because caused by the medical instrument pollution used according to statistics, therefore is made
For medical, particularly portable high molecular material, there is antibacterial biological compatible polymeric material to be for surface or interface introducing
Improve the most important means of medical material anti-microbial property.
It using atom transferred free radical living polymerization (ATRP), can be modified, be formed in surface of polymer material covalence graft
Fine and close functional polymer layer.However ATRP grafting is carried out in surface of polymer material, it needs to introduce ATRP on its surface first
Initiator group could realize, such as aromatic polymer surface introduce halogen methyl（—CH2X）.However conventional method is in virtue
Fragrant surface of polymer material introducing initiator activity group is extremely complex, and reaction condition is very harsh.Such as document Journal of Membrane Science446 (2013) 79–91）, report have anti-pollution function polysulfones（PSF）The preparation of film is included such as
Lower step（See Fig. 1）：（1）Polysulfones is initially dissolved in organic solvents, chloroform, with anhydrous stannic chloride（SnCl4）For catalysis
Agent, using trim,ethylchlorosilane（(CH3)3SiCl）And formaldehyde is reacted for reagent, and halogen is introduced on the main chain of all polymer
Methyl（-CH2X）；（2）It is needed after reaction by polymer deposition and purification, removing the toxic of the inside by complex steps urges
Agent and unreacted substance；（3）By novel polymer casting film of the gained main chain containing halogen methyl；（4）By ATRP method in film surface
It is grafted.
Conventional method is disadvantageous in that described in Fig. 1：（1）The reaction, which belongs to, carries out polymer the modified generation master of ontology
Novel polymer of the chain repetitive unit containing halogen methyl consumes a large amount of chloromethyl reagent, and qualitative change has occurred for material, poly- for dissolving
Close the toxic and volatile difficult solvent recovery of object；（2）The catalyst SnCl of use4Toxic facile hydrolysis, post-processing stages hydrolysis life
Into SnO2It is difficult to remove from polymer, catalyst can not recycle and reuse, and be easy to cause environmental pollution；（3）It uses
Reagent trim,ethylchlorosilane is expensive, facile hydrolysis；（4）The reaction is to water sensitive, therefore catalyst and halide reagent requirement are big, with
It avoids reaction being caused to fail because of catalyst and halide reagent failure；（5）Halogen methyl polymerize by Conventional processing methods as shown in Figure 1
The reaction that object carries out surface grafting is only that the surface halogen methyl of material participates in reaction, and the halogen methyl of material internal is not engaged in connecing
Branch polymerization, therefore the halogen methyl that material internal contains not necessarily generates.6）Such as according to documentJournal of Membrane ScienceThe result of study for the PS membrane that 446 (2013) 79-91 are reported shows that preparing chloromethylation using Fig. 1 methods gathers
Closing object institute casting film causes rate and protein retention to be greatly reduced, and illustrates that membrane aperture prepared by novel polymer becomes larger, this method was film-made
More uses toxic reagent, and the program is caused to be not suitable for preparing biological, medical and food-grade membrane material.7）For some polymerizations
Object such as some polyimides kinds, can only be dissolved in phenol solvent, since phenolic compound is more easy to that halomethylation occurs,
Fig. 1 the methods are not particularly suited for this kind of fragrant high molecular material.
Invention content
The purpose of the invention is to overcome in above-mentioned conventional fragrant polymer film method of modifying to make in ontology modifying process
With organic solvent, the ZnCl to water sensitive2Or SnCl4, expensive organochlorosilane (CH3)3The compounds such as SiCl introduce halogen first
The drawbacks of base.Halogen methyl is introduced by phase transfer catalysis process, and then be grafted stain-proofing layer as shown in Figure 2 the present invention provides a kind of
New method.Original polymer material is first processed and formed a film by this method, in water using phase-transfer-catalyzed reactions, is realized only in fragrance
The surface of polymer film introduces halogen methyl, and then high-efficiency environment friendly is grafted anti-fouling material in polymer surfaces ATRP.
In order to realize foregoing invention task, the present invention is using the technical solution as described in Fig. 2：
Method is as follows：
A kind of preparation method of aromatic polymer anti-soil film, includes the following steps：
The first step introduces halogen methyl in polymer film surface：
Aromatic polymer film is put into reactor, formaldehyde, phase transfer catalyst and saturation halogen acids are added in, 20 ~ 100oC
Reaction 1-12 hours, obtaining surface grafting has the polymer film of halogen methyl, is rinsed repeatedly with deionized water；
Second step, in surface grafting functional polymer, this step can be used following two catalyst system and catalyzings and realize：
Option A：The polymer film that above-mentioned surface is introduced into halogen methyl is put into reaction vessel, will under nitrogen or argon gas atmosphere
The catalyst copper (II) of certain mol proportion, ligand, reducing agent, concentration are mixed more than 0.5 mol/L acrylic ester compound monomers
It closes, solvent is the arbitrary than mixture of water, methanol, ethyl alcohol or three, and 0.5-24h is stirred to react at 25-100 DEG C, later will
The film of modification takes out from reaction system, then is rinsed repeatedly with reaction dissolvent and obtain surface soiling film product.
Option b：The polymer film that above-mentioned surface is introduced into halogen methyl is put into reaction tube, under nitrogen or argon gas atmosphere, by one
Catalyst copper (I), ligand and the concentration for determining molar ratio are mixed more than 0.5 mol/L acrylic ester compounds monomer, and solvent is
Water, methanol, ethyl alcohol or three it is arbitrary than mixture, 0.5-24h is stirred to react at 25-100 DEG C, later by the film of modification from
It is taken out in reaction system, then is rinsed repeatedly with above-mentioned solvent and obtain surface soiling film product.
Polymer film described in the method for the present invention contains including ultrafiltration membrane, NF membrane, reverse osmosis membrane, forward osmosis membrane or all kinds of surfaces
The composite membrane of aromatic polymer.
Aromatic polymer of the present invention includes polysulfones, polyether sulfone, polyimides, polyetherimide, poly aromatic amide and gathers
Aryl ether ketone, polystyrene, the copolymer of aromatic polyester class or above-mentioned polymer or blend etc..
It is in the reaction condition of film surface grafting halomethyl groups in preparation method of the present invention：Formaldehyde, phase transfer catalyst, saturation
The ratio of halogen acids is 1 ~ 3g：0.05~0.2g：10-40mL, 25-100 DEG C of reaction temperature, reaction time 1-12 h.
Phase transfer catalyst of the present invention includes the compound such as lower structure：
R and R in equation 1 above and 21To be less than the saturated hydrocarbons group of 18 carbon atoms；The integer that n in equation 1 above, 2 and 3 is 1-6.
Halogen acids of the present invention includes hydrobromic acid, hydrochloric acid or its mixture.
Option A reaction condition is in film surface progress grafting functional polymer in preparation method of the present invention：Copper（II）Catalyst：Match
Body：Reducing agent, monomer molar ratio are 1:2~3:1：50 ~ 1000, acrylic ester monomer concentration is more than 0.5mol/L, and solvent is
Water, methanol, ethyl alcohol or three it is arbitrary than mixture, 25-100 DEG C of reaction temperature, reaction time 0.5-24h obtains anti-soil film.
Film is washed with solvent three times, save it in for use in water after reaction.
The reaction condition of option b is in film surface progress grafting functional polymer in preparation method of the present invention：Copper（I）Catalyst,
Ligand, monomer molar ratio are 1:2~3:50 ~ 1000, acrylic ester monomer concentration is more than 0.5mol/L, and solvent is water, first
Alcohol, ethyl alcohol or three it is arbitrary than mixture, 25-100 DEG C of reaction temperature, reaction time 0.5-24h obtains anti-soil film.Reaction
After with solvent wash Modified Membrane three times, save it in for use in water.
Copper of the present invention（II）Catalyst includes copper bromide, copper chloride and all kinds of water-soluble cupric salts；Copper（I）Catalysis
Agent includes cuprous bromide, stannous chloride and all kinds of water-soluble cuprous salts.
Ligand of the present invention includes 2,2- bipyridyls or derivatives thereof, 1,2,4,7,10,10- hexamethyl triens
Or derivatives thereof be used as ligand.
Reducing agent of the present invention is glucose, formaldehyde, acetaldehyde or vitamin C.
Acyclic compound monomer of the present invention includes following one or more：
（1）Acrylic acid sulfonic group betaines compound
X is the integer of 2-10 in above formula, and y 2,3 or 4, R are hydrogen or methyl.
（2）Acrylic acid phosphate betaines compound
X is the integer of 2-18 in above formula, and R is hydrogen or methyl.
（3）Acrylic acid carbonyldioxy betaines compound
X is the integer of 2-4 in above formula, and y 1,2 or 3, R are hydrogen or methyl.
（4）Acrylic acid contains-CH2CH2O- structural compounds
N is integer more than 1 in above formula, and R is hydrogen or methyl, R1For hydrogen or ethyl.
（5）Acrylic acid contains-CHOHCH2OH structural compounds
N is the integer more than 1 in above formula, and R is hydrogen or methyl.
Solvent of the present invention compares mixture including water, methanol, ethyl alcohol and three kinds of any of compound.
（1）The halomethylation of the method for the present invention occurs over just film surface, therefore reagent consumption is greatly reduced, and is done using halogen acids
Halide reagent, price are low.
（2）Halomethylation reaction directly is carried out to fragrant film surface in phase transfer method water phase, tradition is avoided to use organic solvent pair
Polymer body carries out the reaction of halomethylation, is not related to the problems such as organic solvent recycles, therefore reduce cost, reduces ring
The probability of border pollution.
（3）Halomethylation of the present invention can directly remove film from phase transfer reaction system after reaction, without tradition
Must be by polymer separating-purifying after halomethylation in method the step of, and phase transfer system can recycle the halogen of next batch
Methylation reaction, therefore cost can be greatly reduced.
（4）Phase transfer catalyst used in the present invention is environmental-friendly stabilization organic compound, can be recycled, hence it is evident that be better than
Tradition is to water sensitive, it is difficult to the SnCl recycled4Wait lewis acid catalysts.
（5）The present invention can carry out halomethylation to the surface of any polymer for having an aromatic structure, have wide applicability.
Film raw material used in the present invention, can both be prepared by classical way, can also buy commodity fragrance film, and then using this
Method prepares anti-soil film.
In addition to fragrant membrane material, other aromatic polymers similar with the method for the present invention are such as products such as medical fragrant high molecular materials
Surface soiling modification, the protection domain that will also fall into this patent are carried out after phase transfer catalysis (PTC) introduces halogen methyl.
Description of the drawings
Fig. 1 is conventional method in aromatic polymer surface grafting（FP represents functional polymer）.
Fig. 2 introduces halogen methyl group and graft-modification method for phase transfer catalysis process polymer surfaces.（1’）Film forming；（2’）Phase transfer
It is catalyzed halomethylation；（3’）It is graft-polymerized；FP represents functional polymer.
Fig. 3 is the size of contact angle before and after PEK-C membrane modifyings in embodiment 1.a）(71.6 °) before modified；b）It is modified
(29.2°)。
Fig. 4 is the variation of antibacterial ability before and after PEK-C membrane modifyings in embodiment 1.A) before modified；B) it is modified
Fig. 5 is hydrophilic variation before and after PSF film surface grafting glycine betaines in embodiment 2.a）Before modified；b）It is modified.
Fig. 6 is the variation of antibacterial ability before and after PSF membrane modifyings in embodiment 2.A) it is modified；B) it is modified.
Specific embodiment
The method of the present invention is further elaborated with reference to specific embodiment.
Embodiment 1：
1）By 18 g phenolphthalein type polyarylether ketone（PEK-C）It pours into round-bottomed flask, it is rear to add in 2 g polyethylene glycol（PEG-600）Add
Add agent and 80 g N-N, dimethylacetylamide（DMAC）Solvent, 24 h of quick stirring and dissolving, obtains yellow transparent at 60 DEG C
Polymer solution；By above-mentioned resulting polymers solution in 24 h of vacuum defoamation；Resulting polymers solution is slowly poured on cleaning
On glass plate, knifing speed is adjusted to 1.87 ms/min, scrapes 150 μ m-thicks（Thickness of liquid film）Film, wait for 8 s in air
It is quickly put into 15 DEG C of deionized water coagulating bath afterwards, is taken out after film Automatic-falling, deionized water is immersed in after cleaning
In it is spare after 24 h.
2）Prepared above by phase inversion 2 square centimeters of PEK-C ultrafiltration membrane films are put into reactor, it is more to add in 2.0 g
Polyformaldehyde, 0.15 g catalyst, 30 mL concentrated hydrochloric acids.Reaction temperature is arranged on 70 DEG C, and 6 h of reaction time, concussion reaction obtains
Surface grafting has the ultrafiltration membrane of chloromethyl.Chloromethylation poly(aryl ether ketone) ultrafiltration membrane obtained is cleaned repeatedly with deionized water.
3）Surface carries out ATRP graft reactions：By 0.0089 g brominations copper powders, 0.0125 g 2,2- bipyridyls and 1.68 g
Methacrylic acid carboxylic acid glycine betaine is put into polymer reactor, then with the ultrafiltration membrane for being grafted with chloromethyl by 4 ml methanols with going
Ionized water by volume 1:It is added in after 1 mixing in 50 milliliters of polymerization pipe.Separately 0.0760 g vitamin Cs are put into small test tube,
And with 1 mL deionized water dissolvings.High pure nitrogen is passed through in polymer reactor and small test tube respectively, keeps 30 min of nitrogen blowing
Afterwards, under nitrogen atmosphere, the polymerization seal of tube is placed in stirring by the vitamin c solution for pipetting 100 μ L with syringe in polymerization pipe
On device, 6 h are stirred to react at being 70 DEG C in temperature；Pollution-resistant membrane obtained is cleaned three times with deionized water after reaction.
PEK-C films are obviously improved through the hydrophily of antifouling film surface that the above method is modified, and the contact angle of original membrane is 71.5o,
The PEK-C films contact angle for being grafted beet base material is 29.2o.Fig. 4 antibacterial experiments show film surface adherency bacterium reduce 90% with
On.
Embodiment 2：
After preparing polysulphone super-filter membrane by phase inversion identical in embodiment 1, impregnated spare after 24 h in deionized water.
1）The polysulfones that will be prepared above by phase inversion（PSF）Ultrafiltration membrane is put into reaction tube, 1.5 g paraformaldehydes of addition,
0.05 g catalyst, 40 mL concentrated hydrochloric acids.Reaction temperature is arranged on 70 DEG C, and 4 h of reaction time, having obtained surface grafting has chloromethane
The ultrafiltration membrane of base.Chloromethyl polysulphone ultrafiltration membrane obtained is cleaned repeatedly with deionized water.
2）By above-mentioned 2 square centimeters of surfaces chloromethylation PSF ultrafiltration membranes, 0.0072g cuprous bromides powder, 0.0125 g 2,2-
Bipyridyl and 1.68 g sulfonic groups glycine betaines are put into polymerization pipe, then by 4 ml methanols with going with the ultrafiltration membrane for being grafted with chloromethyl
Ionized water by volume 1:1 mixed solution is added in 50 milliliters of polymerization pipe.High pure nitrogen is passed through polymerization pipe respectively, is protected
After holding 30 min of nitrogen blowing, the seal of tube will be polymerize, 6 h are stirred to react at being 70 DEG C in temperature, it after reaction will be obtained anti-
Polluted membrane is cleaned with deionized water.
PSF films are obviously improved through the hydrophily of antifouling film surface that the above method is modified, as shown in figure 5, original membrane contact angle is
85.4o, the PSF films contact angle of grafting beet base material is 26.6o.Fig. 6 antibacterial experiments show that the bacterium of film surface adherency is reduced
More than 90%.
Claims (10)
1. a kind of preparation method of aromatic polymer anti-soil film, includes the following steps：
Aromatic polymer film is put into reactor by the first step, formaldehyde, phase transfer catalyst and saturation halogen acids is added in, certain
At a temperature of reaction a period of time after, obtaining surface grafting has the polymer film of halogen methyl, is rinsed repeatedly with deionized water；
Second step is in surface grafting functional polymer：
The polymer film that above-mentioned surface is introduced into halogen methyl by option A is put into reaction vessel, under nitrogen or argon gas atmosphere, by one
Catalyst copper (II), ligand, the reducing agent of molar ratio, acrylic ester compound monomer and solvent mixing are determined, in certain temperature
Under be stirred to react a period of time after, the film of modification is taken out from reaction system, then rinsed with above-mentioned solvent and prevented repeatedly
Dirty film；
The polymer film that above-mentioned surface is introduced into halogen methyl by option b is put into reaction vessel, under nitrogen or argon gas atmosphere, by one
Determine catalyst copper (I), ligand, acrylic ester compound monomer and the solvent mixing of molar ratio, stirring is anti-at a certain temperature
After a period of time, the film of modification should be taken out from reaction system, then rinsed repeatedly with above-mentioned solvent and obtain anti-soil film.
A kind of 2. preparation method of aromatic polymer anti-soil film according to claim 1, which is characterized in that the polymerization
Object film includes ultrafiltration membrane, NF membrane, reverse osmosis membrane, forward osmosis membrane or all kinds of surfaces the composite membrane containing aromatic polymer.
A kind of 3. preparation method of aromatic polymer anti-soil film according to claim 1, which is characterized in that the fragrance
Polymer includes polysulfones, polyether sulfone, polyimides, polyetherimide, poly aromatic amide and poly(aryl ether ketone), polystyrene, fragrance
Copolymer or blend of polyesters or above-mentioned polymer etc..
A kind of 4. preparation method of aromatic polymer anti-soil film according to claim 1, which is characterized in that the preparation
The reaction condition of film surface grafting halogen methyl is in method：Formaldehyde, phase transfer catalyst, saturation halogen acids ratio be 1 ~ 3g：
0.05~0.2g：10-40mL, reaction temperature 20 ~ 100oC, reaction time 1-12 h;Halogen acids include hydrobromic acid, hydrochloric acid or
Its mixture.
5. the preparation method of a kind of aromatic polymer anti-soil film according to claim 1, which is characterized in that the phase turns
Shifting catalyst includes the compound such as lower structure：
R and R in equation 1 above and 21To be less than the saturated hydrocarbons group of 18 carbon atoms；The integer that n in equation 1 above, 2 and 3 is 1-6.
A kind of 6. preparation method of aromatic polymer anti-soil film according to claim 1, which is characterized in that surface grafting work(
Can polymer strategy A reaction conditions be：Copper（II）Catalyst, ligand, reducing agent, monomer molar ratio be 1:2~3:1：50~
1000, acrylic ester monomer concentration is more than 0.5mol/L, solvent is water, methanol, ethyl alcohol or three it is arbitrary than mixture, instead
Answer 25-100 DEG C of temperature, reaction time 0.5-24h.
A kind of 7. preparation method of aromatic polymer anti-soil film according to claim 1, which is characterized in that surface grafting work(
Can polymer strategy B reaction conditions be：Copper（I）Catalyst, ligand, monomer molar ratio are 1:2~3：50 ~ 1000, acrylate
Class monomer concentration is more than 0.5mol/L, and solvent is the arbitrary than mixture, reaction temperature 25-100 of water, methanol, ethyl alcohol or three
DEG C, reaction time 0.5-24h.
A kind of 8. preparation method of aromatic polymer anti-soil film according to claim 1, which is characterized in that the copper
(II) catalyst includes copper bromide, copper chloride or all kinds of water soluble bivalent nantokites；Described copper (I) catalyst includes protobromide
Copper, stannous chloride or all kinds of water-soluble cuprous salts.
A kind of 9. preparation method of aromatic polymer anti-soil film according to claim 1, which is characterized in that the ligand
Including 2,2- bipyridyls or derivatives thereof, 1,2,4,7,10,10- hexamethyl triens or derivatives thereof;Reducing agent is
Glucose, formaldehyde, acetaldehyde or vitamin C.
A kind of 10. preparation method of aromatic polymer anti-soil film according to claim 1, which is characterized in that described third
Olefin(e) acid ester type compound monomer includes following one or more：
（1）Acrylic acid sulfonic group betaines compound
X is the integer of 2-10 in above formula, and y 2,3 or 4, R are hydrogen or methyl;
（2）Acrylic acid phosphate betaines compound
X is the integer of 2-18 in above formula, and R is hydrogen or methyl;
（3）Acrylic acid carbonyldioxy betaines compound
X is the integer of 2-4 in above formula, and y 1,2 or 3, R are hydrogen or methyl;
（4）Acrylic acid contains-CH2CH2O- structural compounds
N is integer more than 1 in above formula, and R is hydrogen or methyl, R1For hydrogen or ethyl;
（5）Acrylic acid contains-CHOHCH2OH structural compounds
N is the integer more than 1 in above formula, and R is hydrogen or methyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341072.6A CN108201793A (en) | 2017-05-16 | 2017-05-16 | A kind of preparation method of aromatic polymer anti-soil film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341072.6A CN108201793A (en) | 2017-05-16 | 2017-05-16 | A kind of preparation method of aromatic polymer anti-soil film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108201793A true CN108201793A (en) | 2018-06-26 |
Family
ID=62604371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710341072.6A Pending CN108201793A (en) | 2017-05-16 | 2017-05-16 | A kind of preparation method of aromatic polymer anti-soil film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108201793A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759785A (en) * | 2020-12-31 | 2021-05-07 | 宁波长阳科技股份有限公司 | Antifogging self-cleaning polyimide film and preparation method thereof |
| CN118161996A (en) * | 2024-04-08 | 2024-06-11 | 江苏中连碧水环境科技有限公司 | Method for modifying aromatic polyamide composite membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090235625A1 (en) * | 2007-09-28 | 2009-09-24 | General Electric Company | Filter and associated method |
| CN104069753A (en) * | 2014-07-15 | 2014-10-01 | 哈尔滨工业大学（威海） | Preparation method for pollution-resistant polymer membrane |
| CN104194027A (en) * | 2014-09-18 | 2014-12-10 | 哈尔滨工业大学（威海） | Preparation method for polymer biochip with biological pollution resistance |
-
2017
- 2017-05-16 CN CN201710341072.6A patent/CN108201793A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090235625A1 (en) * | 2007-09-28 | 2009-09-24 | General Electric Company | Filter and associated method |
| CN104069753A (en) * | 2014-07-15 | 2014-10-01 | 哈尔滨工业大学（威海） | Preparation method for pollution-resistant polymer membrane |
| CN104194027A (en) * | 2014-09-18 | 2014-12-10 | 哈尔滨工业大学（威海） | Preparation method for polymer biochip with biological pollution resistance |
Non-Patent Citations (2)
| Title |
|---|
| 尚洁等: "磺酸内铵盐催化烷基苯的氯甲基化反应", 《分子催化》 * |
| 李佳倓: "芳香类聚合物防污膜的表面改性及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759785A (en) * | 2020-12-31 | 2021-05-07 | 宁波长阳科技股份有限公司 | Antifogging self-cleaning polyimide film and preparation method thereof |
| CN118161996A (en) * | 2024-04-08 | 2024-06-11 | 江苏中连碧水环境科技有限公司 | Method for modifying aromatic polyamide composite membrane |
| CN118161996B (en) * | 2024-04-08 | 2024-08-02 | 江苏中连碧水环境科技有限公司 | Method for modifying aromatic polyamide composite membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6060450B2 (en) | Hydrophilic modified fluorinated membrane (IV) | |
| CN104069753B (en) | A kind of preparation method of antipollution polymeric film | |
| JP6124162B2 (en) | Hydrophilic modified fluorinated membrane (III) | |
| CN108201793A (en) | A kind of preparation method of aromatic polymer anti-soil film | |
| Gebru et al. | Humic acid removal using cellulose acetate membranes grafted with poly (methyl methacrylate) and aminated using tetraethylenepentamine | |
| TWI574841B (en) | Hydrophilically modified fluorinated membrane (i) | |
| CN107081079A (en) | A kind of preparation method and application of efficient hydrophilic modification antipollution poly (ether sulfone) film | |
| CN105504299A (en) | Method for synthesizing ABA type polysulfone family block copolymers | |
| CN111617644B (en) | Preparation method of monolithic polyaryletherketone bipolar membrane with side chain containing porphyrin water dissociation catalytic group | |
| TWI617602B (en) | Hydrophilic porous polytetrafluoroethylene membrane (i) | |
| CN101570597B (en) | Chloracetylating method of poly aryl ether ketone containing fluorine | |
| CN112126093A (en) | Super-hydrophobic antibacterial polypropylene film and preparation method thereof | |
| CN103193941A (en) | Polyether sulfone copolymer modified by sulphobetaine metacrylic acid ester as well as preparation method and application of polyether sulfone copolymer | |
| CN108623811A (en) | One kind containing POSS structure ultralow dielectric poly aryl ether ketone polymers and preparation method thereof | |
| TWI585132B (en) | Hydrophilically modified fluorinated membrane (ii) | |
| Ran et al. | Constructing functional ionic membrane surface by electrochemically mediated atom transfer radical polymerization | |
| CN108203517A (en) | A kind of preparation method of aromatic polymer material surface grafted cation fungistatic coating | |
| CN114588844B (en) | Application of double-sided hollow fiber membrane reactor in Suzuki-Miyaura reaction and membrane reactor thereof | |
| JP2005154742A (en) | Film-like material, its manufacturing method and its use | |
| Wu et al. | Kinetic study of phenol recovery using phase-transfer catalysis in horizontal membrane reactor | |
| CN110841601B (en) | Beta-cyclodextrin dimer for removing organic pollutants in water and preparation and use methods thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180626 |