CN108384019A - A kind of porous organic supermolecular polymer and its preparation method and application - Google Patents

A kind of porous organic supermolecular polymer and its preparation method and application Download PDF

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Publication number
CN108384019A
CN108384019A CN201810176049.0A CN201810176049A CN108384019A CN 108384019 A CN108384019 A CN 108384019A CN 201810176049 A CN201810176049 A CN 201810176049A CN 108384019 A CN108384019 A CN 108384019A
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polymer
porous
porous organic
preparation
organic supermolecular
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武凯
平巍
程聪
吴彦
谢昆
程启洪
姜明
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Chongqing Three Gorges University
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Chongqing Three Gorges University
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    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention belongs to heterocyclic compound technical field, a kind of porous organic supermolecular polymer and its preparation method and application is disclosed, zinc nitrate 1.5g distillation water dissolutions is weighed, weighs terephthalic acid (TPA) 0.8g identical with the amount of nitric acid zinc material；20mL distilled water is added, concentrated ammonia liquor is added dropwise and is stirred continuously, until terephthalic acid (TPA) thoroughly reacts dissolving, zinc nitrate solution is added, it is 6.6 7.5 to be used in combination the dust technology of 0.01mol/L to adjust mixed solution pH value；Mixed solution is poured into 250mL conical flasks, bottleneck is sealed with plastic fresh-keeping membrane, baking oven is put into and heats 4 8h, takes out and cooled to room temperature is placed 7~20 days at a temperature of 0 10 DEG C, clear colorless crystals shape organic porous polymer self-organizing generates.The porous organic supermolecular polymer technology effect of the present invention is unique, and method is easy, and synthesis cost is cheap, economical and practical.

Description

A kind of porous organic supermolecular polymer and its preparation method and application
Technical field
The invention belongs to heterocyclic compound technical field more particularly to a kind of porous organic supermolecular polymer and its preparations Methods and applications.
Background technology
Currently, the prior art commonly used in the trade is such：
Porous organic supermolecular polymer is a kind of novel porous material, in heterogeneous catalysis, absorption, separation and gas Storage etc. has potential application.Modern society's energy consumption is huge, and largely discharge is considered as global change to carbon dioxide One of warm reason, but currently capture CO2Method need to expend big energy.Porous organic polymer material is in greenhouse gases dirt There are prodigious potentiality on the problems such as dye and lack of energy.Porous material develops to certainly via traditional zeolite molecular sieve at present It is main to construct organic nano porous polymer using methodology of organic synthesis.
In conclusion the technical issues of this programme can solve：
(1) under normal pressure, the material of absorption carbon dioxide is prepared by hydro-thermal reaction using simple organic matter.
(2) it avoids using autoclave, the danger that may be brought.
(3) sorbing material prepared self-organizing under 0-10 DEG C of low temperature synthesizes, and realizes porous organic polymer material Low temperature synthesis technique.
Solve the difficulty and meaning of above-mentioned technical problem：It is moreThe specific surface of hole organic supermolecular polymer material Yin Qigao The skeleton structure of long-pending, high physical and chemical stability, lightweight becomes CO2The important materials of adsorbing domain.
Invention content
In view of the problems of the existing technology, the present invention provides a kind of porous organic supermolecular polymer and its preparation sides Method and application.
The invention is realized in this way a kind of preparation method of porous organic supermolecular polymer, described porous organic super The preparation method of Molecularly Imprinted Polymer includes the following steps：
Step 1 weighs zinc nitrate 1.5g distillation water dissolutions, weighs terephthaldehyde identical with the amount of nitric acid zinc material Sour 0.8g；
Step 2 is added 20mL distilled water, concentrated ammonia liquor is added dropwise and is stirred continuously, until terephthalic acid (TPA) thoroughly reacts molten Zinc nitrate solution is added in solution, and it is 6.6-7.5 to be used in combination the dust technology of 0.01mol/L to adjust mixed solution pH value；
Mixed solution is poured into 250mL conical flasks by step 3, and bottleneck is sealed with plastic fresh-keeping membrane, is put into baking oven heating 4-8h, It takes out and cooled to room temperature is placed 7~20 days, clear colorless crystals shape organic porous polymer at a temperature of 0-10 DEG C Self-organizing generates.Organic porous polymer molecular formula is [C6H8O4·2H2O]∞, belong to supramolecular complex substance, Cambridge number of crystals The porous polymer crystal has been authorized to compile according to library center (the Cambridge Crystallographic Data Centre) Number be CCDC 818556.
Further, the concentrated ammonia liquor 30%, W/W.
Further, 100 DEG C of baking oven heating 4-8h are put into.
Another object of the present invention is to provide a kind of preparation method preparations by the porous organic supermolecular polymer Porous organic supermolecular polymer.
Another object of the present invention is to provide a kind of porous organic supermolecular polymer to adsorb and trap dioxy Change the application in terms of carbon.
It is described to make another object of the present invention is to provide a kind of application method of the porous organic supermolecular polymer Include with method：First porous organic supermolecular polymer is dried in air atmosphere at room temperature, then 10g is taken to dry Sample be put into CO2In gas, pressurization is adsorbed.
In conclusion advantages of the present invention and good effect are：
With the method phase of the porous organic supermolecular polymer of conventional synthesis：First, preparation method of the invention need not be It is carried out under high temperature and pressure, autoclave need not be used, avoid the danger that high temperature and pressure may be brought.Second, the present invention The solvent used in preparation method only has water, other organic reagents need not be used, if sorbing material ought largely be prepared by avoiding When, it may be caused damages to environment using organic solvent.
The porous organic supermolecular polymer technology effect of the present invention is unique, and method is easy, and synthesis cost is cheap, economical real Favour.
In order to characterize the performance for adsorbing carbon dioxide of porous organic supermolecular polymer prepared by the present invention, we will be real The data result that test obtains is analyzed, and obtains the titanium dioxide that every gram of porous organic supermolecular polymer is adsorbed under different pressures Carbon molecules number, is shown in Table 1：
The CO of every gram of coordination polymer absorption when 1 difference relative pressure of table2Molecular number
Relative standard's atmospheric pressure (Pr) 0.031 0.099 0.160 0.252 0.400 0.549 0.699 0.819 0.899 0.973
Adsorbance (× 1023)/molecular number 0.279 0.550 0.843 1.590 2.341 3.107 3.944 4.326 4.894 5.151
Description of the drawings
Fig. 1 is the preparation method flow chart of porous organic supermolecular polymer provided in an embodiment of the present invention.
Fig. 2 is the molecules align accumulation graph of porous organic polymer provided in an embodiment of the present invention.
Fig. 3 is pore-size distribution situation schematic diagram provided in an embodiment of the present invention.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
The specific surface area of porous organic supermolecular polymer material Yin Qigao of the present invention, high physical and chemical stability, The skeleton structure of lightweight becomes CO2The important materials of adsorbing domain.
As shown in Figure 1, the preparation method of porous organic supermolecular polymer provided in an embodiment of the present invention includes following step Suddenly：
S101：Zinc nitrate 1.5g (0.005mol) is weighed with a small amount of distillation water dissolution.Weigh the amount phase with nitric acid zinc material Same terephthalic acid (TPA) 0.8g (0.005mol)；
S102：20mL distilled water is added, concentrated ammonia liquor (30%, W/W) is added dropwise and is stirred continuously, until terephthalic acid (TPA) Thoroughly reaction dissolving, is added above-mentioned zinc nitrate solution, and it is 6.6- to be used in combination the dust technology of 0.01mol/L to adjust mixed solution pH value Between 7.5；
S103：Mixed solution is poured into 250mL conical flasks, bottleneck is sealed with plastic fresh-keeping membrane, is put into 100 DEG C of baking oven heating 4- 8h, takes out and cooled to room temperature is placed 7~20 days, clear colorless crystals shape Porous-Organic under 0-10 DEG C of environment temperature Polymer self-organization generates.
The drying of porous organic supermolecular polymer provided in an embodiment of the present invention：It is dry in air atmosphere at room temperature. Absorption：The sample that 10g has been dried is taken to be put into CO2In gas, pressurization is adsorbed.
The application principle of the present invention is further described with reference to specific embodiment.
Porous organic supermolecular crystal preparation process provided in an embodiment of the present invention：1, zinc nitrate 1.5g is weighed (0.005mol) distills water dissolution with a small amount of.Weigh terephthalic acid (TPA) 0.8g identical with the amount of nitric acid zinc material (0.005mol) is then added 20mL distilled water, concentrated ammonia liquor (30%, W/W) is added dropwise and is stirred continuously, until terephthaldehyde Sour thoroughly reaction dissolving, is added above-mentioned zinc nitrate solution, and it is 6.6- to be used in combination the dust technology of 0.01mol/L to adjust mixed solution pH value Between 7.5.Mixed solution is poured into 250mL conical flasks, bottleneck is sealed with plastic fresh-keeping membrane, 100 DEG C of baking oven heating 4-8h is put into, takes Go out and cooled to room temperature is placed 7~20 days under 0-10 DEG C of environment temperature, the polymerization of clear colorless crystals shape Porous-Organic Object self-organizing generates.
It is dry：It is dry in air atmosphere at room temperature.
Absorption：The sample that 10g has been dried is taken to be put into CO2In gas,
Experiment metal zinc salt used can be zinc nitrate, and zinc chloride can also be the soluble zinc salts such as zinc sulfate.
In order to characterize the performance for adsorbing carbon dioxide of porous organic supermolecular polymer prepared by the present invention, we will be real The data result that test obtains is analyzed, and obtains the titanium dioxide that every gram of porous organic supermolecular polymer is adsorbed under different pressures Carbon molecules number, is shown in Table 1：
The CO of every gram of coordination polymer absorption when 1 difference relative pressure of table2Molecular number
Relative standard's atmospheric pressure (Pr) 0.031 0.099 0.160 0.252 0.400 0.549 0.699 0.819 0.899 0.973
Adsorbance (× 1023)/molecular number 0.279 0.550 0.843 1.590 2.341 3.107 3.944 4.326 4.894 6.151
The specific surface area of porous organic polymer is characterized using specific surface area adsorption instrument, pore-size distribution situation is shown in Fig. 3.
Fig. 2 is the molecules align accumulation graph of porous organic polymer provided in an embodiment of the present invention.
Fig. 3 is pore-size distribution situation schematic diagram provided in an embodiment of the present invention.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.

Claims (6)

1. a kind of preparation method of porous organic supermolecular polymer, which is characterized in that the porous organic supermolecular polymer Preparation method include the following steps：
Step 1 weighs zinc nitrate 1.5g distillation water dissolutions, weighs terephthalic acid (TPA) identical with the amount of nitric acid zinc material 0.8g；
Step 2 is added 20mL distilled water, concentrated ammonia liquor is added dropwise and is stirred continuously, until terephthalic acid (TPA) thoroughly reacts dissolving, Zinc nitrate solution is added, it is 6.6-7.5 to be used in combination the dust technology of 0.01mol/L to adjust mixed solution pH value；
Mixed solution is poured into 250mL conical flasks by step 3, and bottleneck is sealed with plastic fresh-keeping membrane, is put into baking oven heating 4-8h, is taken out And cooled to room temperature is placed 7~20 days at 0-10 DEG C, clear colorless crystals shape organic porous polymer self-organizing generates； Organic porous polymer molecular formula is [C6H8O4·2H2O]∞。
2. the preparation method of porous organic supermolecular polymer as described in claim 1, which is characterized in that the concentrated ammonia liquor 30%, W/W.
3. the preparation method of porous organic supermolecular polymer as described in claim 1, which is characterized in that be put into 100 DEG C of bakings Case heats 4-8h.
4. porous organic supermolecular prepared by a kind of preparation method of organic supermolecular polymer porous described in claim 1 gathers Close object.
5. a kind of application of porous organic supermolecular polymer as claimed in claim 4 in terms of adsorbing and trapping carbon dioxide.
6. a kind of application method of porous organic supermolecular polymer as claimed in claim 4, which is characterized in that the user Method includes：It is dry in air atmosphere at room temperature：The sample that 10g has been dried is taken to be put into CO2In gas, pressurization is adsorbed.
CN201810176049.0A 2018-03-02 2018-03-02 A kind of porous organic supermolecular polymer and its preparation method and application Pending CN108384019A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014057504A1 (en) * 2012-10-12 2014-04-17 Council Of Scientific & Industrial Research Porous crystalline frameworks, process for the preparation therof and their mechanical delamination to covalent organic nanosheets (cons)
CN105504121A (en) * 2015-12-09 2016-04-20 中盈长江国际新能源投资有限公司 Porous silica gel supported ionic liquid polymer for adsorbing CO2 and preparation method thereof
CN106268690A (en) * 2016-08-31 2017-01-04 北京化工大学 A kind of for carbon dioxide adsorption and framework material separated and preparation method thereof
CN106693601A (en) * 2015-11-12 2017-05-24 中国科学院大连化学物理研究所 Method used for adsorbing iodine with covalent organic framework material
CN107362785A (en) * 2017-07-18 2017-11-21 华南师范大学 A kind of covalently organic frame bonded silica gel stationary phase and its application of the chirality of hydrazone key connecting-type

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014057504A1 (en) * 2012-10-12 2014-04-17 Council Of Scientific & Industrial Research Porous crystalline frameworks, process for the preparation therof and their mechanical delamination to covalent organic nanosheets (cons)
CN106693601A (en) * 2015-11-12 2017-05-24 中国科学院大连化学物理研究所 Method used for adsorbing iodine with covalent organic framework material
CN105504121A (en) * 2015-12-09 2016-04-20 中盈长江国际新能源投资有限公司 Porous silica gel supported ionic liquid polymer for adsorbing CO2 and preparation method thereof
CN106268690A (en) * 2016-08-31 2017-01-04 北京化工大学 A kind of for carbon dioxide adsorption and framework material separated and preparation method thereof
CN107362785A (en) * 2017-07-18 2017-11-21 华南师范大学 A kind of covalently organic frame bonded silica gel stationary phase and its application of the chirality of hydrazone key connecting-type

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
武凯: "《对煤层气（甲烷）有吸附选择性的材料制备及其吸附性能研究》", 15 January 2007, 中国优秀硕士论文数据库 *

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