CN107519849A - A kind of amination has microporous polymer adsorbent and its application certainly - Google Patents
A kind of amination has microporous polymer adsorbent and its application certainly Download PDFInfo
- Publication number
- CN107519849A CN107519849A CN201710973199.XA CN201710973199A CN107519849A CN 107519849 A CN107519849 A CN 107519849A CN 201710973199 A CN201710973199 A CN 201710973199A CN 107519849 A CN107519849 A CN 107519849A
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- China
- Prior art keywords
- microporous polymer
- amination
- adsorbent
- polymer adsorbent
- filter cake
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of amination from having microporous polymer adsorbent and its application, belong to sorbing material preparation field, it is using tetrahydrofuran borane complex as reducing agent, by from the cyano reduction having on microporous polymer into amino, and obtains the adsorbent.The present invention adds its activity group content, so as to improve the absorption property of adsorbent, it is can be used for the absorption of dyestuff, especially anionic dye in environmental water sample by introducing a large amount of amino from tool microporous polymer.
Description
Technical field
The invention belongs to sorbing material preparation field, and in particular to a kind of amination from have microporous polymer adsorbent and its
Using.
Background technology
Azo dyes species is various, comprising alkalescence, acidity, reactive dye etc., is widely used in the works such as weaving, cosmetics
Industry.Although azo dyes makes our life become colorful in riotous profusion, it fact proved, the water pollution brought by these dyestuffs has
Make that organism is carcinogenic, the harm such as pathogenic.Therefore need badly and prevented and treated by a kind of economically viable method.
Now, the method for removing dyestuff from water body has the methods of physics, chemistry and biology, wherein absorption is the simplest
One of single, efficient method.Porous material has first due to having the characteristics that specific surface area is big, hole is more in adsorption applications
Its advantage.According to the literature, the increase means such as specific surface area or effective adsorption site significantly improve material absorption property
Common method.From tool microporous polymer（PIMs）It is that a kind of free volume is high, specific surface area is big, strong to organic matter affinity more
Pore polymer, it is widely used in the fields such as gaseous jet simulation, organic matter absorption, heterogeneous catalysis and hydrogen storage.Because PIMs is with more
Pore structure and chemically be modified the features such as, its be also used as remove dyestuff new material.Such as Satilmis monoethanolamines
With diethanol amine be modified PIM-1 can in 72 h selective absorption anionic dye.And it there is no at present on to micro- from having
Pore polymer carries out amination and for the report of adsorpting anion dyestuff.
The content of the invention
It is an object of the invention to provide a kind of amination from tool microporous polymer adsorbent and its application, the ammonia provided
Baseization is bonded firm, property stabilization from having microporous polymer sorbing material, and containing a large amount of active groups, adsorption capacity is larger, for
The adsorption and enrichment ability of dyestuff is good in environment.
To achieve the above object, the present invention adopts the following technical scheme that：
From having microporous polymer adsorbent, it is using tetrahydrofuran borane complex as reducing agent, to micro- from having for a kind of amination
Pore polymer is reduced, and the amination is made from tool microporous polymer adsorbent；Its preparation method is that 2.0 g are micro- from having
Pore polymer is in 130 mL tetrahydrofurans（THF）In be evenly stirred until and be completely dissolved after, nitrogen is passed through, after it is cooled to 0 DEG C
Stir 15 min；Then under the conditions of enclosed system, magnetic agitation, 25 mL tetrahydrofuran borane complexes are slowly added dropwise, afterwards
It is transferred in water-bath, under the conditions of nitrogen protection, magnetic agitation, 60 DEG C of condensing refluxes react 12 h；Question response terminates rear cold
But to room temperature, 80 mL ethanol is added dropwise and remove excess borane, stirs after solution-stabilized, filters to obtain filter cake；Then by filter cake
Add in the mol/L methanolic HCl solutions of 120 mL 1.0, after the h of magnetic agitation 12, filter, be washed to neutrality；Filter cake is added again
Enter after stirring 3 h in the sodium hydroxide solution of 200 mL mass concentrations 5%, filter, be washed to neutrality, product is in 110 DEG C of air blast
12 h are dried, produce the adsorbent.
Wherein, the preparation method from tool microporous polymer is：By 5.1062 g 5,5,6,6- tetrahydroxy -3,3,3,
The double indanes of 3- tetramethyl -1,1- spirals（TTSBI）With 3.0013 g tetrafluoro terephthalonitriles（TFTPN）It is dissolved in 100 mL N.N- bis-
NMF（DMF）In, nitrogen is passed through, it is anhydrous to add 5.1248 g to after being completely dissolved for magnetic agitation under the conditions of 65 DEG C
K2CO3, continue at 65 DEG C of magnetic agitations under nitrogen protection and react 72 h；Question response is cooled to room temperature after terminating, and reaction solution is fallen
Enter in 150 mL deionized waters, suction filtration obtains filter cake；Gained filter cake min of magnetic agitation 15 in 350 mL deionized waters, then take out
After filter, filter cake is in 110 DEG C of h of forced air drying 12, then successively with 300 mL Isosorbide-5-Nitraes-dioxane, 100 mL acetone, 200 mL
Deionized water and the washing of 100 mL acetone, filter, are most made after 110 DEG C of h of forced air drying 12.
The amination can be used for dyestuff, especially anionic dye in environmental water sample from having microporous polymer adsorbent
Absorption.
The remarkable advantage of the present invention is：
（1）The present invention using tetrahydrofuran borane complex is reducing agent, by from the cyano reduction ammonification having on microporous polymer
Base, good stability is made it have, and which introduce a large amount of amino groups, and combined from the absorption work(for having microporous polymer
Can, its adsorption capacity can be significantly improved；
（2）The amination that the present invention synthesizes has the advantages of adsorption capacity is big from having microporous polymer adsorbent, can be used as environment
The adsorbent of dyestuff in water sample, the absorption for the anionic dye that is particularly suitable for use in.
Brief description of the drawings
Fig. 1 is preparation principle figure of the amination of the present invention from tool microporous polymer adsorbent.
Fig. 2 is different pH value to NH2- PIM-1 adsorbs the influence situation map of sunset yellow performance.
Fig. 3 is NH2The adsorption effect figures of-the PIM-1 to various concentrations sunset yellow.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Preparation of the amination of embodiment 1 from tool microporous polymer adsorbent
（1）From tool microporous polymer PIM-1 synthesis：By 5.1062 g（15 mmol）TTSBI and 3.0013 g（15
mmol）TFTPN is dissolved in 100 mL DMF, is passed through nitrogen, and magnetic agitation adds to after being completely dissolved under the conditions of 65 DEG C
5.1248 g anhydrous Ks2CO3, continue at 65 DEG C of magnetic agitations under nitrogen protection and react 72 h；Question response is cooled to room after terminating
Temperature, reaction solution is poured into 150 mL deionized waters, suction filtration obtains filter cake；Afterwards in 500 mL beakers, by gained filter cake in
The min of magnetic agitation 15 in 350 mL deionized waters, then after filtering, filter cake is then used successively in 110 DEG C of h of forced air drying 12
300 mL Isosorbide-5-Nitraes-dioxane, 100 mL acetone, 200 mL deionized waters and the washing of 100 mL acetone, are filtered, most after 110
DEG C forced air drying 12 h, it is standby；
（2）Amination has microporous polymer NH certainly2- PIM-1 synthesis：2.0 g PIM-1 are stirred in 130 mL THF
It is even to be passed through nitrogen to after being completely dissolved, stir 15 min after it is cooled to 0 DEG C；Then in enclosed system, magnetic agitation bar
Under part, 25 mL tetrahydrofuran borane complexes are slowly added dropwise, are transferred to afterwards in water-bath, in nitrogen protection, magnetic agitation bar
Under part, 60 DEG C of condensing refluxes react 12 h；Question response is cooled to room temperature after terminating, and 80 mL ethanol are added dropwise and remove excessive boron
Alkane, stir after solution-stabilized, filter to obtain filter cake；Then filter cake is added in the mol/L methanolic HCl solutions of 120 mL 1.0,
After the h of magnetic agitation 12, filter, be washed to neutrality；Filter cake is added again in the sodium hydroxide solution of 200 mL mass concentrations 5% and stirred
After mixing 3 h, filter, be washed to neutrality, product dries 12 h in 110 DEG C of air blast and produces NH2-PIM-1。
Fig. 1 is preparation principle figure of the amination from tool microporous polymer adsorbent.
Influence of the pH value of embodiment 2 to amination from tool microporous polymer adsorbent absorption property
Using the gained NH of embodiment 12- PIM-1 to the sunset yellow in different pH value with entering respectively without amidized PIM-1
Row Static Adsorption is tested, using its absorptivity of determined by ultraviolet spectrophotometry, as a result as shown in Figure 2.The concentration of initial sunset yellow：
100 ppm；Adsorbent amount：5 mg；Duration of oscillation：2 h；Temperature：25℃；Volume of sample：10 mL.
From Figure 2 it can be seen that compared with PIM-1, NH under different pH value2- PIM-1 has preferable adsorptivity to sunset yellow
Energy.
The measure of the saturated adsorption capacity of embodiment 3
Amination is shown in Fig. 3 from having microporous polymer adsorbent to the adsorption effect measurement result of various concentrations sunset yellow.
From the figure 3, it may be seen that when sunset yellow solution is in low concentration, amination is from having microporous polymer adsorbent to sunset yellow
Adsorption capacity increase with the increase of its concentration, there is platform when initial concentration reaches 150mg/g, illustrate adsorbent to up to
Saturation state is arrived, now amination is 348.16 mg/ to the saturated adsorption capacity of sunset yellow from having microporous polymer adsorbent
g。
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (3)
1. a kind of amination has microporous polymer adsorbent certainly, it is characterised in that：Using tetrahydrofuran borane complex as reducing agent,
To being reduced from tool microporous polymer, the amination is made from tool microporous polymer adsorbent.
2. amination according to claim 1 has microporous polymer adsorbent certainly, it is characterised in that：Its preparation method is
By 2.0 g from having after microporous polymer is evenly stirred until in 130 mL tetrahydrofurans and is completely dissolved, nitrogen is passed through, treats that its is cold
But to stirring 15 min after 0 DEG C；Then under the conditions of enclosed system, magnetic agitation, 25 mL tetrahydrofuran borines are slowly added dropwise
Complex compound, it is transferred to afterwards in water-bath, under the conditions of nitrogen protection, magnetic agitation, 60 DEG C of condensing refluxes react 12 h；Treat
Reaction is cooled to room temperature after terminating, and 80 mL ethanol are added dropwise and remove excess borane, stir after solution-stabilized, filtering to filter
Cake；Then filter cake is added in 120 mL, 1.0 mol/L methanolic HCl solutions, after the h of magnetic agitation 12, filtered, in being washed to
Property；Again by filter cake add 200 mL, mass concentration 5% sodium hydroxide solution in stir 3 h after, filter, be washed to neutrality, produce
Thing dries 12 h in 110 DEG C of air blast, produces the adsorbent.
3. a kind of amination as claimed in claim 1 has the application of microporous polymer adsorbent certainly, it is characterised in that：For ring
The absorption of dyestuff in the water sample of border.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019182A (en) * | 2019-12-25 | 2020-04-17 | 天津大学 | Preparation method of polymer anion exchange membrane with micropores |
| CN112521596A (en) * | 2019-09-18 | 2021-03-19 | 中国科学院大连化学物理研究所 | Sulfydryl functionalized self-possessed microporous polymer and preparation and application thereof |
| WO2022121101A1 (en) * | 2020-12-09 | 2022-06-16 | 苏州大学 | Method for separating dye-containing wastewater based on porous polymer-modified metal carbon nanotube composite membrane |
Citations (2)
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|---|---|---|---|---|
| CN105792919A (en) * | 2013-12-16 | 2016-07-20 | 沙特基础工业全球技术公司 | Treated mixed matrix polymeric membranes |
| CN106674560A (en) * | 2016-12-13 | 2017-05-17 | 西安交通大学 | Crown ether micropore containing polyimide intrinsic microporosity polymer membrane and preparation method thereof |
-
2017
- 2017-10-18 CN CN201710973199.XA patent/CN107519849B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105792919A (en) * | 2013-12-16 | 2016-07-20 | 沙特基础工业全球技术公司 | Treated mixed matrix polymeric membranes |
| CN106674560A (en) * | 2016-12-13 | 2017-05-17 | 西安交通大学 | Crown ether micropore containing polyimide intrinsic microporosity polymer membrane and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BEKIR SATILMIS ET AL.: "Hydroxyalkylaminoalkylamide PIMs: Selective Adsorption by Ethanolamine- and Diethanolamine-Modified PIM‑1", 《MACROMOLECULES》 * |
| HASMUKH A. PATEL ET AL.: "Noninvasive functionalization of polymers of intrinsic microporosity for enhanced CO2 capture", 《CHEM. COMMUN.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521596A (en) * | 2019-09-18 | 2021-03-19 | 中国科学院大连化学物理研究所 | Sulfydryl functionalized self-possessed microporous polymer and preparation and application thereof |
| CN112521596B (en) * | 2019-09-18 | 2021-09-28 | 中国科学院大连化学物理研究所 | Sulfydryl functionalized self-possessed microporous polymer and preparation and application thereof |
| CN111019182A (en) * | 2019-12-25 | 2020-04-17 | 天津大学 | Preparation method of polymer anion exchange membrane with micropores |
| CN111019182B (en) * | 2019-12-25 | 2022-10-11 | 天津大学 | Preparation method of polymer anion exchange membrane with micropores |
| WO2022121101A1 (en) * | 2020-12-09 | 2022-06-16 | 苏州大学 | Method for separating dye-containing wastewater based on porous polymer-modified metal carbon nanotube composite membrane |
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Granted publication date: 20190405 Termination date: 20211018 |