CN1772796A - Prepn process of positively charged hybrid organic-inorganic film - Google Patents
Prepn process of positively charged hybrid organic-inorganic film Download PDFInfo
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Abstract
The preparation process of positively charged hybrid organic-inorganic film features that benzyl bromide substituted polyphenyl ether, aminoalkyl silone and tertiary amine are first stirred in solvent to react to obtain the mixed solution containing positively charged sol-gel reaction precursor and unreacted aminoalkyl silone; water and catalyst are then added to make the precursor and the unreacted aminoalkyl silone produce sol-gel reaction; and through further coating and drying, the positively charged hybrid organic-inorganic film is produced. The preparation process of the present invention is fast and simple, and adopts easy-to-obtain material and no seriously toxic material; and the prepared positively charged hybrid organic-inorganic film has well compatible organic phase and inorganic phase, high organic phase content, great varying range and high heat resistance.
Description
Technical field:
The invention belongs to the membrane technique field, particularly relate to the method for sol-gel method preparation that adopt based on the hybrid organic-inorganic film of the lotus positive electricity of polyphenylene oxide (PPO).
Background technology:
Aspects such as the recovery of Positively charged membrane useful metal in as seawater (slightly salty) desalination, tap water hard-off, sewage, electrophoretic paint waste water processing, electrochemical sensor have a wide range of applications.At present widely used is lotus positive electricity organic polymer material film, because organic materials self, common physical strength of these films and chemical stability are relatively poor, scarcely high temperature resistant, soda acid and organic solvent, thus limited application in some field.An approach that improves these defectives of lotus positive electricity organic membrane is that inorganic materials physical strength and good stability, chemically-resistant and advantages such as biological attack, long service life are fused in organic Positively charged membrane material, promptly prepares the hybrid inorganic-organic materials film of lotus positive electricity.
U.S. Pat 6,201,051 has reported that the sol gel reaction product with the alkoxide of polyfunctional group organosilicon or B, Al, Si, Sn, Ti or Zr mixes with lotus positive electricity organic polymer, or B, Al, Si, Sn, Ti or Zr, oxide compound mix with lotus positive electricity organic polymer, obtain can be used as the positively charged hybrid organic-inorganic material of coating.Because this method adopts mechanical blending, does not carry out chemically crosslinked, does not have strong chemical b ` between inorganic component and the organic lotus positive electricity component in the system, consistency is relatively poor relatively.
" membrane science magazine " (Journal of Membrane Science that Holland publishes, 1997,126,161-169) and " chemical material " (Chemistry of Materials of publishing of the U.S., 2001,13,1124-1130) reported and adopt the small molecules organoalkoxysilane of lotus positive electricity to carry out sol gel reaction, behind the inorganic matrix top coat, prepare the method for lotus positive electricity hybridized film.This preparation method is a raw material with the small molecules organoalkoxysilane, and sol-gel resultant organic component content is less, and snappiness is not high, thereby has limited the Application Areas of this lotus positive electricity hybridized film.
" membrane science magazine " (Journal of Membrane Science, 2003,216 (1-2), 269-278) reported that the organoalkoxysilane that will contain primary amine and secondary amine group earlier is linked on the end capped peg molecule chain of isocyanide ester base by hydrogen transfer reactions, make resultant carry out sol gel reaction then, quaternized again after filming, obtain positively charged hybrid organic-inorganic film.But prepare in this method and will use the bigger TDI of toxicity in the hybridized film process.
Chinese patent application number 03132271.9 has been announced a kind of preparation method of positively charged hybrid organic-inorganic film, multiple functional radical organoalkoxysilane and the macromolecular compound that contains ester group or epoxy side group or end group are carried out aminolysis, alcoholysis or ring-opening reaction, then resultant is carried out quaterisation, obtain lotus positive electricity sol gel reaction precursor; Though it is poor that the prepared lotus positive electricity hybridized film of this method has overcome between organic phase and the inorganic phase consistency, the snappiness of film is the defective on the high-technology not, and also avoided using the bigger material of toxicity in the preparation process of film, but precursor preparation needs two-step reaction.
" membrane science magazine " (Journal of Membrane Science, 2001,190:159-166) reported and directly undertaken quaternary ammoniated for polyphenylene oxide (BPPO) by Trimethylamine 99 with bromotoluene, the preparation Positively charged membrane, the Positively charged membrane of this preparation belongs to organic homogeneous-phase anion exchange film category, owing to do not introduce inorganic composition, the poor heat resistance of film.
Summary of the invention:
The invention provides a kind of preparation method of positively charged hybrid organic-inorganic film, overcoming the above-mentioned defective of prior art, for the preparation of lotus positive electricity hybridized film provides a more simple and direct approach.
The preparation method of positively charged hybrid organic-inorganic film of the present invention, it is characterized in that under protection of inert gas, in solvent, in molar ratio is 1 for polyphenylene oxide (BPPO) with amino-alkyl silicane and tertiary amine with bromotoluene: 1-3: 0.2-1 carried out stirring reaction 4-12 hour, the concentration of BPPO in system is 0.015-0.045g/mL, obtains containing the mixing solutions of lotus positive electricity sol gel reaction precursor and unreacted amino-alkyl silicane; Add entry again and as the hydrochloric acid of catalyzer, making with the amino-alkyl silicane of initial add-on calculating and the mol ratio of water and catalyzer is 1: 3: 0.001-0.01, under 40-80 ℃ of condition, stir, make precursor and unreacted amino-alkyl silicane carry out sol gel reaction; Gained colloidal sol is filmed on matrix; Diaphragm is dried under room temperature environment and forms uniform and stable gel coat; In 60-150 ℃ of environment, continue to be dried to constant weight then, promptly obtain positively charged hybrid organic-inorganic film.
Described amino-alkyl silicane, its chemical formula can be expressed as [X R
1Y R
2]
4-pSiY "
pOr [XR
1]
4-pSiY "
p, wherein X, Y are respectively primary amine, secondary amine group, R
1And R
2" be the alkoxy grp of carbon, the span of p is the integer of 1-3 to be alkyl or aryl, Y.
Described tertiary amine comprises Trimethylamine 99, triethylamine, tripropyl amine and Tributylamine.
Described dissolvant of reaction system is selected from N, dinethylformamide (DMF) and chlorobenzene, N, N-diethyl acetamide (DMAc) and chlorobenzene, methyl-sulphoxide (DMSO) and chlorobenzene, or tetrahydrofuran (THF) (THF) and/or 1-Methyl-2-Pyrrolidone.
Described matrix is polyfluortetraethylene plate, Al
2O
3Microfiltration membrane or Al
2O
3Ultra-filtration membrane.
The present invention takes to utilize the primary amine group of benzyl bromine group on the macromolecular chain and amino-alkyl silicane to react on macromolecular compound BPPO chain in the grafting amino-alkyl silicane, benzyl bromine group on the macromolecular chain also generates the method for quaternized ammonium groups with reactive tertiary amine, obtain the sol gel reaction precursor of the higher lotus positive electricity of organic content, carry out sol gel reaction with this precursor and amino-alkyl silicane again, thereby make positively charged hybrid organic-inorganic film.With U.S. Pat 6,201, the 051 positively charged hybrid organic-inorganic material compared of taking that inorganic and organic composition are carried out the blend technique preparation, because to have chemical bond to link between inorganic silicon oxide components and the organic composition in the hybridized film of the inventive method preparation, consistency is better; With " membrane science magazine " (Journal of Membrane Science, 1997,126,161-169), " chemical material " (Chemical material, 2001,13,1124-1130) report is that raw material carries out the method that sol gel reaction prepares lotus positive electricity hybridized film and compares with the small molecules organoalkoxysilane, and sol gel reaction precursor of the present invention is a macromolecular compound, organic content can be higher, and ratio can be regulated; With " membrane science magazine " (Journal of Membrane Science, 2003,216 (1-2), 269-278) report is alkoxy silane cross linked to the end capped peg molecule chain of isocyanide ester base with small molecules, carry out sol gel reaction again, the quaternized method that obtains lotus positive electricity hybridized film in back of filming is compared, and the present invention prepares and need not the compound that adopts toxicity bigger in the lotus positive electricity hybridized film process; With Chinese patent application number 03132271.9 report multiple functional radical organoalkoxysilane and the macromolecular compound that contains ester group are carried out aminolysis reaction, carrying out the method that quaterisation, sol gel reaction obtain lotus positive electricity hybridized film then compares, raw material sources of the present invention are more direct, and step is more terse.With " membrane science magazine " (Journal of Membrane Science, 2001,190:159-166) report carries out the quaternary ammoniated method that prepare Positively charged membrane for polyphenylene oxide (BPPO) by Trimethylamine 99 with bromotoluene and compares, contain inorganic component in the prepared positively charged hybrid organic-inorganic film of the present invention, the thermotolerance of film is better.
Embodiment:
Further describe the preparation method of positively charged hybrid organic-inorganic film of the present invention by the following examples.
Embodiment 1. is with reactant ratio BPPO: γ-An Bingjisanjiayangjiguiwan (A1110): Trimethylamine 99=1: 1: 1 preparation positively charged hybrid organic-inorganic film
Employing is equipped with the magneton agitator, is had the 100ml three-necked flask of nitrogen inlet and dropping funnel, add N, dinethylformamide (DMF) and chlorobenzene, the DMF solution that under the condition of logical nitrogen, adds γ-An Bingjisanjiayangjiguiwan (A1110) and Trimethylamine 99 (TMA) respectively, under agitation drip the chlorobenzene solution of bromotoluene then, stirring reaction under the room temperature for polyphenylene oxide (BPPO).The volume ratio of DMF and chlorobenzene is 1: 1, and the mol ratio of each component is BPPO (calculating with a brominated structures unit): A1110: TMA=1: 1: 1, the concentration of BPPO in mixing solutions was 0.045g/mL.
After reaction is carried out 4 hours, take out partially mixed solution and precipitate with normal hexane, washing is after drying for several times, to remove unreacted A1110 and TMA, obtains the precursor of hybridized film, and it is carried out infrared analysis and nuclear magnetic resonance spectroscopy.
In the mixing solutions that contains lotus positive electricity sol gel reaction precursor and unreacted A1110 of reaction gained, stir and add hydrochloric acid and deionized water down, carry out sol gel reaction, wherein the mol ratio of A1110 (calculating with add-on), hydrochloric acid, water is A1110: HCl: H
2O=1: 0.003: 3., after 12 hours sol solutions is coated on the polyfluortetraethylene plate at 60 ℃ of stirring reactions, room temperature was placed after 48 hours, placed 24 hours under 150 ℃ environment again.The film that obtains is scraped from polyfluortetraethylene plate with scalpel, it is carried out infrared and hot analytical test.
Sol solutions is poured in the glass surface ware, getting a diameter is 5 centimetres, the surface mean pore size is that 0.2 micron aluminium sesquioxide sheet soaked in this colloidal sol 15 seconds, at room temperature placed after the upset 12 hours, then after placing 24 hours under 150 ℃ of environment, measure gained diaphragm-operated loading capacity, be the rejection of 4 gelatin solution to the pH value of 1g/L with ordinary method, and scanning electron microscopic observation is carried out on gained diaphragm-operated surface.
Among the precursor infrared test result, 1030-1120cm
-1The strong characteristic peak of the newly-increased Si in place, 1604,1466cm
-1There are the charateristic avsorption band of phenyl ring, 1189cm in the place
-1There is the ether peak at the place.This shows that the benzyl bromine group on the polymer BPPO chain takes place really with the graft reaction that contains the A1110 of primary amine group.The infrared test result of hybridized film is except 1030-1120cm
-1Outside the characteristic peak of the Si of place strengthens, similar with the precursor peaks type, show that the film of preparation contains phenyl ring, there is the Si component simultaneously in organic compositions such as ether, are organic-inorganic hybrid.
The nuclear magnetic resonance spectroscopy of precursor shows that reactant B PPO disappears at the brooethyl peak of～4.4 chemical shifts place, shows that the benzyl bromine group on the polymer BPPO chain all reacts.
Hot analytical results shows that the gained hybridized film begins near 190 ℃ weightless.
Scanning electron microscope observation shows that gained hybridized film surfacing homogeneous has a spot of white small-particle, shows that organic and inorganic component compatibility is fine in the hybrid material that makes, and is not separated.
The anion-exchange capacity (IEC) that loading capacity is measured prepared hybridized film is 119.4mmol/m
2, the pH value is to the rejection (R)=0.99 of gelatin solution under 4 the condition.
The above analysis result, the diaphragm that obtains of present embodiment is the hybrid organic-inorganic film of lotus positive electricity as can be known, and to compare thermostability better with organic Positively charged membrane.
Embodiment 2. is with reactant ratio BPPO: γ-An Bingjisanjiayangjiguiwan: Trimethylamine 99=3: 3: 1 preparation positively charged hybrid organic-inorganic films
Adopt device and the operating process identical with embodiment 1, the mol ratio of regulating BPPO, γ-An Bingjisanjiayangjiguiwan and Trimethylamine 99 is BPPO: γ-An Bingjisanjiayangjiguiwan: Trimethylamine 99=3: 3: 1, the BPPO concentration in mixing solutions is 0.03g/mL.Reaction is carried out carrying out sol gel reaction after 6 hours, makes the hybrid organic-inorganic film of lotus positive electricity.
The anion-exchange capacity that records gained lotus positive electricity hybridized film is 85.6mmol/m
2, to the rejection R=0.89 of the gelatin solution of the 1g/L of pH=4.
Embodiment 3. is with reactant ratio BPPO: γ-An Bingjisanjiayangjiguiwan: Trimethylamine 99=5: 5: 1 preparation positively charged hybrid organic-inorganic films
Adopt device and the operating process identical with embodiment 1, the mol ratio of regulating BPPO, γ-An Bingjisanjiayangjiguiwan and Trimethylamine 99 is BPPO: γ-An Bingjisanjiayangjiguiwan: Trimethylamine 99=5: 5: 1, the BPPO concentration in mixing solutions is 0.025g/mL.Reaction is carried out carrying out sol gel reaction after 6 hours, makes the hybrid organic-inorganic film of lotus positive electricity.
The anion-exchange capacity that records gained lotus positive electricity hybridized film is 58.9mmol/m
2, to the rejection R=0.88 of the gelatin solution of the 1g/L of pH=4.
Embodiment 4. is with reactant ratio BPPO: γ-An Bingjisanjiayangjiguiwan: triethylamine=2: 2: 1 preparation positively charged hybrid organic-inorganic films
Employing is equipped with the magneton agitator, is had the 100ml three-necked flask of nitrogen inlet and dropping funnel, add N, N-N,N-DIMETHYLACETAMIDE (DMAc) and chlorobenzene, under the condition of logical nitrogen, add γ-An Bingjisanjiayangjiguiwan (A1110) and triethylamine respectively, under agitation drip the chlorobenzene solution of bromotoluene then, stirring reaction under the room temperature for polyphenylene oxide (BPPO).The volume ratio of DMAc and chlorobenzene is 1: 1, and the mol ratio of each component is BPPO (calculating with a brominated structures unit): A1110: triethylamine=2: 2: 1, the BPPO concentration in mixing solutions is 0.03g/mL.
After reaction is carried out 8 hours, in the mixing solutions that contains lotus positive electricity sol gel reaction precursor and unreacted A1110 of reaction gained, stir adding hydrochloric acid and deionized water down, carry out sol gel reaction.The mol ratio of A1110 (calculating with add-on), hydrochloric acid, water is A1110: HCl: H
2O=1: 0.03: 3.Stirring reaction is 12 hours under 60 ℃ of conditions, and all the other experimental installations and operating process make the hybrid organic-inorganic film of lotus positive electricity with embodiment 1.
The anion-exchange capacity that records gained lotus positive electricity hybridized film is 90.4mmol/m
2, to the rejection R=0.84 of the gelatin solution of the 1g/L of pH=4.
Embodiment 5. is with reactant ratio BPPO: γ-An Bingjisanjiayangjiguiwan: Tributylamine=4: 4: 1 preparation positively charged hybrid organic-inorganic films
Employing is equipped with the magneton agitator, is had the 100ml three-necked flask of nitrogen inlet and dropping funnel, add tetrahydrofuran (THF), under the condition of logical nitrogen, add γ-An Bingjisanjiayangjiguiwan (A1110) and Tributylamine respectively, under agitation drip the tetrahydrofuran solution of bromotoluene then, stirring reaction under the room temperature for polyphenylene oxide (BPPO).The mol ratio of each component is BPPO (calculating with a brominated structures unit): A1110: Tributylamine=4: 4: 1, the BPPO concentration in mixing solutions is 0.03g/mL.
After reaction is carried out 12 hours, in the mixing solutions that contains lotus positive electricity sol gel reaction precursor and unreacted A1110 of reaction gained, stir adding hydrochloric acid and deionized water down, carry out sol gel reaction.The mol ratio of A1110 (calculating with add-on), hydrochloric acid, water is A1110: HCl: H
2O=1: 0.03: 3.Stirring reaction is 12 hours under 60 ℃ of conditions, and all the other experimental installations and operating process make the hybrid organic-inorganic film of lotus positive electricity with embodiment 1.
The anion-exchange capacity that records gained lotus positive electricity hybridized film is 37.2mmol/m
2, to the rejection R=0.72 of the gelatin solution of the 1g/L of pH=4.
In the present embodiment, replace tetrahydrofuran (THF) to make solvent, obtain identical hybrid organic-inorganic film with 1-Methyl-2-Pyrrolidone.
Embodiment 6. is with reactant ratio BPPO: γ-An Bingjisanyiyangjiguiwan: triethylamine=1: 3: 1 preparation positively charged hybrid organic-inorganic film
Employing is equipped with the magneton agitator, is had the 100ml three-necked flask of nitrogen inlet and dropping funnel, add methyl-sulphoxide (DMSO) and chlorobenzene, under the condition of logical nitrogen, add γ-An Bingjisanyiyangjiguiwan and triethylamine respectively, under agitation drip the chlorobenzene solution of bromotoluene then, stirring reaction under the room temperature for polyphenylene oxide (BPPO).The volume ratio of DMSO and chlorobenzene is 1: 1, and the mol ratio of each component is BPPO (calculating with a brominated structures unit): γ-An Bingjisanyiyangjiguiwan: triethylamine=1: 3: 1, the BPPO concentration in mixing solutions is 0.015g/mL.
After reaction is carried out 8 hours, in the mixing solutions that contains lotus positive electricity sol gel reaction precursor and unreacted γ-An Bingjisanyiyangjiguiwan of reaction gained, stir adding hydrochloric acid and deionized water down, carry out sol gel reaction.The mol ratio of γ-An Bingjisanyiyangjiguiwan (calculating with add-on), hydrochloric acid, water is γ-An Bingjisanyiyangjiguiwan: HCl: H
2O=1: 0.003: 3.At 60 ℃ of stirring reactions after 12 hours, sol solutions is poured in the glass surface ware, getting a diameter is 5 centimetres, the surface mean pore size is that 0.2 micron aluminium sesquioxide sheet soaked in this colloidal sol 15 seconds, at room temperature placed after the upset 12 hours, under 60 ℃ of environment, placed 24 hours then, make the hybrid organic-inorganic film of lotus positive electricity.
The anion-exchange capacity that records gained lotus positive electricity hybridized film is 71.3mmol/m
2, to the rejection R=0.79 of the gelatin solution of the 1g/L of pH=4.
Embodiment 7. is with reactant ratio BPPO: N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan (A-1120): Trimethylamine 99=1: 1: 1 preparation positively charged hybrid organic-inorganic film
Adopt device and the operating process identical with embodiment 1, replace γ-An Bingjisanjiayangjiguiwan with N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan (A-1120), and the mol ratio of regulating BPPO, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan and Trimethylamine 99 is 1: 1: 1, and the concentration of BPPO in mixing solutions is 0.04g/mL.Reaction is carried out carrying out sol gel reaction after 6 hours, makes the hybrid organic-inorganic film of lotus positive electricity.
The anion-exchange capacity that records gained lotus positive electricity hybridized film is 121.5mmol/m
2, to the rejection R=0.93 of the gelatin solution of the 1g/L of pH=4.
Claims (5)
1, a kind of preparation method of positively charged hybrid organic-inorganic film, it is characterized in that under protection of inert gas, in solvent, is 1 with bromotoluene in molar ratio for polyphenylene oxide and amino-alkyl silicane and tertiary amine: 1-3: 0.2-1 carried out stirring reaction 4-12 hour, and bromotoluene is 0.015-0.045g/mL for the concentration of polyphenylene oxide in system; Add entry again and as the hydrochloric acid of catalyzer, making with the amino-alkyl silicane of initial add-on calculating and the mol ratio of water and catalyzer is 1: 3: 0.001-0.01, under 40-80 ℃ of condition, stir, make precursor and unreacted amino-alkyl silicane carry out sol gel reaction; Gained colloidal sol is filmed on matrix; Diaphragm is dried under room temperature environment and forms uniform and stable gel coat; In 60-150 ℃ of environment, continue to be dried to constant weight then, promptly obtain positively charged hybrid organic-inorganic film.
2, the preparation method of positively charged hybrid organic-inorganic film according to claim 1 is characterised in that described amino-alkyl silicane, and its chemical formula can be expressed as [X R
1Y R
2]
4-pSiY "
pOr [XR
1]
4-pSiY "
p, wherein X, Y are respectively primary amine, secondary amine group, R
1And R
2" be alkoxy grp, the span of p is the integer of 1-3 to be alkyl or aryl, Y.
3, the preparation method of positively charged hybrid organic-inorganic film according to claim 1 is characterised in that described tertiary amine, comprises Trimethylamine 99, triethylamine, tripropyl amine and Tributylamine.
4, the preparation method of positively charged hybrid organic-inorganic film according to claim 1, be characterised in that described dissolvant of reaction system is selected from N, dinethylformamide and chlorobenzene, N, N-diethyl acetamide and chlorobenzene, methyl-sulphoxide and chlorobenzene, or tetrahydrofuran (THF) and/or 1-Methyl-2-Pyrrolidone.
5, the preparation method of positively charged hybrid organic-inorganic film according to claim 1 is characterised in that described matrix is polyfluortetraethylene plate, Al
2O
3Microfiltration membrane or Al
2O
3Ultra-filtration membrane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220169B (en) * | 2007-09-14 | 2010-09-15 | 中国科学技术大学 | Production method for organic-inorganic hybridization anion exchange membrane |
| CN101845215A (en) * | 2010-04-02 | 2010-09-29 | 中国科学技术大学 | Preparation method based on brominated polyphenylether blending of hybrid anion exchange membrane |
| CN101284216B (en) * | 2008-05-08 | 2011-05-18 | 中国科学技术大学 | Hollow fiber anion-exchange membrane and preparation method thereof |
| CN101775202B (en) * | 2010-02-05 | 2011-09-07 | 山东天维膜技术有限公司 | Method based on sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation-exchange membranes |
-
2004
- 2004-11-13 CN CN 200410065737 patent/CN1301287C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220169B (en) * | 2007-09-14 | 2010-09-15 | 中国科学技术大学 | Production method for organic-inorganic hybridization anion exchange membrane |
| CN101284216B (en) * | 2008-05-08 | 2011-05-18 | 中国科学技术大学 | Hollow fiber anion-exchange membrane and preparation method thereof |
| CN101775202B (en) * | 2010-02-05 | 2011-09-07 | 山东天维膜技术有限公司 | Method based on sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation-exchange membranes |
| CN101845215A (en) * | 2010-04-02 | 2010-09-29 | 中国科学技术大学 | Preparation method based on brominated polyphenylether blending of hybrid anion exchange membrane |
| CN101845215B (en) * | 2010-04-02 | 2011-12-14 | 中国科学技术大学 | Preparation method based on brominated polyphenylether blending of hybrid anion exchange membrane |
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Granted publication date: 20070221 Termination date: 20191113 |