CN113549212A - Novel preparation method of functional polyetherimide additive - Google Patents
Novel preparation method of functional polyetherimide additive Download PDFInfo
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- CN113549212A CN113549212A CN202110885276.2A CN202110885276A CN113549212A CN 113549212 A CN113549212 A CN 113549212A CN 202110885276 A CN202110885276 A CN 202110885276A CN 113549212 A CN113549212 A CN 113549212A
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- 239000000654 additive Substances 0.000 title claims abstract description 33
- 230000000996 additive effect Effects 0.000 title claims abstract description 30
- 239000004697 Polyetherimide Substances 0.000 title claims abstract description 27
- 229920001601 polyetherimide Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 nickel dichlorophthalimide Chemical compound 0.000 claims abstract description 10
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001294 propane Substances 0.000 claims abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- DFOZLRWOCDRNDA-UHFFFAOYSA-N 4,5-dichloroisoindole-1,3-dione Chemical compound ClC1=CC=C2C(=O)NC(=O)C2=C1Cl DFOZLRWOCDRNDA-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- SDTHIDMOBRXVOQ-UHFFFAOYSA-N 5-[bis(2-chloroethyl)amino]-6-methyl-1h-pyrimidine-2,4-dione Chemical compound CC=1NC(=O)NC(=O)C=1N(CCCl)CCCl SDTHIDMOBRXVOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 abstract 1
- LAHJLCQITWMYJW-UHFFFAOYSA-N 4-chloro-6-(dimethylamino)-5-propylisoindole-1,3-dione Chemical compound CCCC(C(Cl)=C(C(C(N1)=O)=C2)C1=O)=C2N(C)C LAHJLCQITWMYJW-UHFFFAOYSA-N 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 27
- 229920002492 poly(sulfone) Polymers 0.000 description 11
- 238000005266 casting Methods 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- BGJNRQSGJHVURK-UHFFFAOYSA-N 5-chloroisoindole-1,3-dione Chemical compound ClC1=CC=C2C(=O)NC(=O)C2=C1 BGJNRQSGJHVURK-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a novel preparation method of a functional polyetherimide additive, which mainly comprises the steps of taking nickel dichlorophthalimide as a raw material, taking aromatic diphenol and dimethylamino-propyl-chlorophthalimide as raw materials, directly preparing a diamino polyetherimide intermediate through aromatic nucleophilic substitution reaction, and then reacting the obtained intermediate with propane sultone or propane lactone to obtain the amphiphilic polyether imide additive for preparing a high-performance antifouling film.
Description
Technical Field
The invention relates to a novel preparation method of a functional polyetherimide additive, belonging to the field of polymer synthetic chemistry.
Background
In order to improve the antifouling performance of the Polysulfone (PSF) ultrafiltration membrane, a physical blending method is adopted, and an amphiphilic component is added into a membrane casting solution, so that the method is a process flow most suitable for industrial production. In recent years, ZL201810028428.5 and Journal of membrane Science,2017(542),81-90 disclose that amphiphilic polyether imide is used as a membrane additive material, the water flux, antifouling property and mechanical property of the membrane are comprehensively improved, and the problem that the antifouling property of the membrane is improved by traditional additives such as polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP) but other mechanical and heat resistance of the membrane is inevitably sacrificed is solved. However, the above-disclosed amphiphilic polyether imide additive materials are prepared by a conventional synthetic route using a dianhydride, a diamine and a capping agent, and the raw material ether dianhydride of the method is generally prepared by the following method of formula 17:
the multistep reaction scheme of formula 17 above is a direct cause of the high cost of the ether dianhydride. Therefore, a new synthetic route is developed to prepare the polyetherimide additive, the synthetic steps are reduced, and the preparation cost can be effectively reduced.
Disclosure of Invention
In order to solve the problem of high cost caused by preparation of polyetherimide through a dianhydride diamine route, the invention discloses a method for preparing a functional polyetherimide additive through aromatic nucleophilic substitution reaction, so that the preparation steps of the additive are reduced, and the cost is greatly reduced. The additive prepared by the invention is added into the membrane casting solution in an amount of 0.5-3%, so that the membrane water flux is greatly improved, the recovery rate is improved to more than 90% from 60% of that of a comparative membrane, the preparation method is simple, the additive is good in compatibility with polysulfone material and difficult to run off, and the price cost is equivalent to that of a polysulfone membrane substrate, so that the additive is very suitable for industrial application.
In order to realize the invention task, the invention adopts the following technical scheme:
a new preparation method of a functional polyetherimide additive is implemented according to the following steps:
n is an integer of 2 to 20, wherein-Ar-is one of the following formulas 1 to 7:
wherein, -Ar' -is one of the following formulas 8-14:
wherein ,
is one of the following formulas 15 or 16:
the preparation process comprises the following steps: under the protection of nitrogen, performing condensation reaction on bischlorophthalimide a, bisphenol b, N-dimethyl-propyl chlorophthalimide c, potassium carbonate, an aprotic solvent and a water-carrying agent toluene or xylene at 130-160 ℃ for 5-24 hours. Filtering to remove insoluble substances while the solution is hot, recovering solvent under reduced pressure, Soxhlet extracting the obtained light yellow solid crude product d with ethanol or isopropanol for 3 hours, drying at 100 ℃ for 6 hours to obtain bisamino polyetherimide d,
dissolving the obtained bisamino polyetherimide d in anhydrous chloroform, adding propane sultone or propane lactone with the same mole number as that of N, N-dimethyl-propyl chlorophthalimide, performing reflux reaction for 5-10 hours, recovering the solvent chloroform, washing the obtained solid substance with deionized water for 3 times, and drying at 100 ℃ for 10 hours to obtain the amphiphilic polyether imide additive e or f.
Further, the bischlorophthalimide monomer a comprises bis (3-bischlorophthalimide) and bis (4-bischlorophthalimide); the molar ratio of the condensing agent potassium carbonate to the bisphenol is 2-2.1: 1.
further, the reaction solvent comprises one of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMF) and dimethyl sulfoxide (DMSO), the using amount of the reaction solvent is 3-5 times of the mass of the reaction monomer, and the added water-carrying agent and the solvent have the same mass; the reaction concentration of the obtained bis-amino polyetherimide d and propane sultone or propane lactone is controlled to be 2-10%.
The technical advantages of the invention are as follows: the invention discloses a method for preparing a functional polyetherimide additive by aromatic nucleophilic substitution reaction, so that the preparation steps of the additive are reduced, and the cost is greatly reduced. The additive prepared by the invention is added into the membrane casting solution in an amount of 0.5-3%, so that the membrane water flux is greatly improved, the recovery rate is improved to more than 90% from 60% of that of a comparative membrane, the preparation method is simple, the additive is good in compatibility with polysulfone material and difficult to run off, and the price cost is equivalent to that of a polysulfone membrane substrate, so that the additive is very suitable for industrial application.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be described in detail with reference to examples, but the present invention is not limited to the scope of the examples.
Example 1
Adding 4, 4' -bis (4-chlorophthalimide) -diphenyl ether (5.29g, 0.01moL), hydroquinone (1.21g, 0.011moL), N- (3-N, N-dimethylamino-propyl) -4-chlorophthalimide (0.523g, 0.002moL), anhydrous potassium carbonate (1.8g, 0.023moL), 30mL anhydrous DMAc and 30mL toluene into a 200mL three-neck flask under nitrogen atmosphere, stirring with water at 130 ℃ for 4 hours, recovering toluene with water, increasing the temperature to 150 ℃, continuing to react for 8 hours, filtering insoluble substances, recovering solvent DMAc from the obtained filtrate under reduced pressure in a round-bottom flask, soxhlet extracting the obtained light yellow solid crude product c with ethanol for 3 hours, drying at 100 ℃ for 6 hours to obtain 5.68g of product d1, dissolving the product d1 in 100g chloroform, adding propane sulfonic acid lactone (0.244g, 0.002moL) for reflux reaction for 5 hours, recovering solvent chloroform, washing the obtained solid substance with deionized water for 3 times, and drying at 100 ℃ for 10 hours to obtain amphiphilic polyether imide additive e 1.
Example 2
Adding 4, 4' -bis (3-chlorophthalimide) -diphenyl sulfone (5.77g, 0.01moL), bisphenol A (2.28g, 0.012moL), N- (3-N, N-dimethylamino-propyl) -4-chlorophthalimide (1.046g, 0.004moL), anhydrous potassium carbonate (1.95g, 0.025moL), 30mL anhydrous DMSO and 30mL xylene into a 200mL three-necked flask under nitrogen atmosphere, stirring with water at 160 ℃ for 2 hours, recovering xylene with water, continuing to react at 150 ℃ for 5 hours, filtering insoluble substances, recovering solvent 488 from the filtrate under reduced pressure in a round-bottomed flask, soxhlet extracting the obtained crude product of pale yellow solid with ethanol for 3 hours, drying at 100 ℃ for 6 hours to obtain 6.40g of product d2, dissolving the product in 80g of chloroform, adding propanesulfonic acid lactone (0.004 g, 0.004moL) and refluxing for 10 hours, recovering solvent chloroform, washing the obtained solid substance with deionized water for 3 times, and drying at 100 ℃ for 10 hours to obtain amphiphilic polyether imide additive e 2.
Example 3
Adding 4,4 ' -bis (4-chlorophthalimide) -3,3 ' -dimethyl-diphenylmethane (5.55g, 0.01moL), 4 ' -biphenol (1.954g,0.0105moL), N- (3-N, N-dimethylamino-propyl) -4-chlorophthalimide (0.261g, 0.001moL), anhydrous potassium carbonate (1.8g, 0.023moL), 28mL of anhydrous DMAc and 28mL of toluene into a 200mL three-necked flask under nitrogen atmosphere, stirring and refluxing at 140 ℃ for 4 hours, recovering toluene with water, continuing stirring at 150 ℃ for 10 hours, filtering insoluble substances, recovering the solvent DMAc from the filtrate in a flask under reduced pressure, soxhlet extracting the obtained light yellow solid crude product c with ethanol for 3 hours, drying at 100 ℃ for 6 hours to obtain 6.20g of product d3, dissolving the product in 80g of chloroform, adding propanesultone (0.244g, 0.002moL) for reflux reaction for 10 hours, recovering solvent chloroform, washing the obtained solid substance with deionized water for 3 times, and drying at 100 ℃ for 10 hours to obtain the amphiphilic polyether imide additive e 3.
Example 4
D 1-d 3 are prepared by the method of the embodiment 1-3, and then the mixture is refluxed and reacted with propiolactone in chloroform for 10 hours to respectively prepare f 1-f 3.
Example 5
Preparation of polysulfone membranes, the feeds are as follows in table 1:
TABLE 1 polysulfone membrane charge ratio
The membrane preparation process is described by taking M1 as an example: 16.8g of anhydrous DMAc, 0.2g of amphiphilic biphenyl polyimide additive e1 and 3.0 g of PSF, heating and stirring at 60 ℃ for 3 hours, and standing and defoaming the casting solution for 24 hours. Controlling the thickness of the film to be 150 micrometers, scraping the film casting solution on a small flat film scraper with the thickness of 25cm X25 cm, transferring the film casting solution to a coagulating bath with the temperature of 25 ℃ within 5 seconds, taking out the film after 1 hour, and soaking the film in ionized water for 24 hours. The film was boiled in boiling water for 3 hours and subjected to a contact angle test, the results of which are shown in Table 2. The water contact angle of the PSF original membrane M0 prepared according to the traditional method is 86 degrees, the contact angle of the modified membranes M1-M6 of the casting solution added with 1% of additives with the cornea is below 66 degrees, the contact angle is reduced by more than 20 degrees, the hydrophilicity of the modified membranes is obviously increased, and the water flux of the modified membranes M1-M6 is increased by more than 40% compared with that of the traditional membrane M1, which shows that the series of additives also have the function of pore-forming.
TABLE 2 Water flux and contact Angle test results for membranes (average of five measurements)
The results show that the water flux and the hydrophilic performance of the polysulfone membrane are improved after the membrane is boiled by high-temperature water by adopting the additive disclosed by the invention, and the additive prepared by the invention can keep the membrane, is difficult to run off and has the characteristics of hydrophilicity and antifouling property.
While the present invention has been described in detail with reference to the specific examples, the description is only for the purpose of understanding the method and the core concept of the present invention, and it should be noted that, for those skilled in the art, various modifications and alterations can be made to the present invention without departing from the principle of the present invention.
Claims (3)
1. A new preparation method of a functional polyetherimide additive is characterized in that the preparation process is as follows:
n is an integer of 2 to 20, wherein-Ar-is one of the following formulas 1 to 7:
wherein, -Ar' -is one of the following formulas 8-14:
wherein ,
is one of the following formulas 15 or 16:
the preparation process comprises the following steps: under the protection of nitrogen, performing condensation reaction on bischlorophthalimide a, bisphenol b, N-dimethyl-propyl chlorophthalimide c, potassium carbonate, an aprotic solvent and a water-carrying agent toluene or xylene at 130-160 ℃ for 5-24 hours. Filtering to remove insoluble substances while the solution is hot, recovering solvent, Soxhlet extracting the obtained light yellow solid crude product d with ethanol or isopropanol for 3 hours, drying at 100 ℃ for 6 hours to obtain the bis-amino polyetherimide d,
dissolving the obtained bisamino polyetherimide d in anhydrous chloroform, adding propane sultone or propane lactone with the same mole number as that of N, N-dimethyl-propyl chlorophthalimide, performing reflux reaction for 5-10 hours, recovering solvent chloroform, washing the obtained solid substance with deionized water for 3 times, and drying at 100 ℃ for 10 hours to obtain the amphiphilic polyether imide additive e or f.
2. The method for preparing a functional polyetherimide additive according to claim 1, wherein the bischlorophthalimide monomer a comprises bis (3-bischlorophthalimide) and bis (4-bischlorophthalimide); the molar ratio of the condensing agent potassium carbonate to the bisphenol b is 2-2.1: 1.
3. the novel preparation method of the functional polyetherimide additive according to claim 1, characterized in that the reaction solvent comprises one of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMF) and dimethyl sulfoxide (DMSO), the amount of the reaction solvent is 3-5 times of the mass of the reaction monomer, and the added water-carrying agent and the solvent have the same mass; the reaction concentration of the obtained bis-amino polyetherimide d and propane sultone or propane lactone is controlled to be 2-10%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560113A (en) * | 2004-02-23 | 2005-01-05 | 中国科学院长春应用化学研究所 | Process of preparing polyether imide by titanium dichloride imide and diphenol |
| CN1803888A (en) * | 2005-12-26 | 2006-07-19 | 中国科学院长春应用化学研究所 | Method for preparing polyether imide copolymer by bisubstituted compound and bisphenol |
| CN108203510A (en) * | 2018-01-12 | 2018-06-26 | 哈尔滨工业大学（威海） | A kind of preparation method for the betaine type polyimides additive being modified for supermicro filtration membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560113A (en) * | 2004-02-23 | 2005-01-05 | 中国科学院长春应用化学研究所 | Process of preparing polyether imide by titanium dichloride imide and diphenol |
| CN1803888A (en) * | 2005-12-26 | 2006-07-19 | 中国科学院长春应用化学研究所 | Method for preparing polyether imide copolymer by bisubstituted compound and bisphenol |
| CN108203510A (en) * | 2018-01-12 | 2018-06-26 | 哈尔滨工业大学（威海） | A kind of preparation method for the betaine type polyimides additive being modified for supermicro filtration membrane |
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