CN106432563B - A kind of preparation method of super large pore polymer material - Google Patents
A kind of preparation method of super large pore polymer material Download PDFInfo
- Publication number
- CN106432563B CN106432563B CN201610816150.9A CN201610816150A CN106432563B CN 106432563 B CN106432563 B CN 106432563B CN 201610816150 A CN201610816150 A CN 201610816150A CN 106432563 B CN106432563 B CN 106432563B
- Authority
- CN
- China
- Prior art keywords
- super large
- large pore
- polymer material
- hours
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F112/36—Divinylbenzene
-
- 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
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of preparation methods of super large pore polymer material.This method is using divinylbenzene as monomer, and using dimethyl sulfoxide (DMSO) as solvent, crystal is pore-foaming agent, selects redox initiation system, polymerize to obtain super large pore polymer by cryogenic freezing.Preparation method of the present invention is simple and reliable, and post-processing is simple, and the polymer of gained has super large pore structure, its pore diameter range is mainly distributed between 5 ~ 100 nm and 20 ~ 200 μm, with adsorption capacity height, the fast feature of the rate of adsorption can reach 32.9 g/g to the adsorbance of crude oil.
Description
Technical field
Application the present invention relates to a kind of preparation method of super large pore polymer material and in crude oil absorption, belongs to high score
Sub- field of material technology.
Background technology
In recent years, with the rapid development of industry, countries in the world increasingly increase the demand of oil, in opening for oil
During adopting, refine, store and transporting, a large amount of greasy dirts enter marine systems, cause marine environmental pollution, wherein with work
The pollution that industry waste oil and oil spilling are brought is the most serious.
To solve the problems, such as this, various countries' researcher develops a series of high oil-absorbing resin in succession.High oil-absorbing resin
It is the low crosslinking degree polymer being made of lipophile monomer, there is three-dimensional net structure identical with high hydroscopic resin, pass through tree
The Van der Waals force generated between the lipophilic group segment and oil molecule of fat intramolecular realizes oil suction effect.CN103203226A discloses one
Kind Graphite powder-butyl rubber composite frozen gel oil absorption material and preparation method thereof, using butyl rubber as basis material, with S2Cl2
For crosslinking agent, using benzene or hexamethylene as solvent, crystal is pore-foaming agent, and graphite powder is added, anti-under the conditions of -5 DEG C ~ -2 DEG C
It answers, obtains the gel rubber material with three-dimensional netted pore structure, pore-size distribution is between 20 ~ 50 μm, to diesel oil, crude oil, lubrication
The maximal absorptive capacity of oil is respectively 18.66 g/g, 19.86 g/g, 19.50 g/g.CN104672372A discloses a kind of high suction
Oleoresin and preparation method thereof, using ethylacrylic acid hexadecyl ester as monomer, using glycol diacrylate as crosslinking agent, with over cure
Sour sodium and sodium sulfite are redox initiator, and Tween 80 is emulsifier, and resin, gained resin pair are obtained by emulsion polymerization
Tetrachloromethane is absorbed as 45 times, is absorbed as 20 times to crude oil, oil suction saturation time is 15 minutes.CN101891860B is announced
A kind of porous high oil absorption resin and preparation method thereof, using styrene and dodecylacrylate as polymerized monomer, with two
Ethenylbenzene is crosslinking agent, and butyl acetate is pore-foaming agent, using sodium peroxydisulfate as initiator, is prepared for inhaling by the method for suspension polymerisation
Oleoresin, gained resin adsorption is after 24 hours, the maximal absorptive capacity to gasoline and jet fuel be respectively 19.2 g/g and
14.1 g/g.More than, gained resin is all relatively low to the adsorbance of crude oil, and oil suction saturation time is longer, and swelling rate is slow.
Invention content
For above-mentioned limitation, present invention proposition uses dimethyl sulfoxide (DMSO) for solvent, and crystal is pore-foaming agent, by low
The method of warm freezing polymerization prepares super large pore polymer material, and uses it in the adsorption applications to crude oil.
The technical scheme is that:
A kind of preparation method of super large pore polymer material, steps are as follows：
It takes a certain amount of monomer to be dissolved in solvent, sequentially adds n,N-Dimethylaniline and benzoyl peroxide, concussion is mixed
It is even, it after leading to nitrogen 5 min removing oxygen, goes in syringe, seals, freezed 24 hours at -18 DEG C, go to anti-at 4 DEG C
It answers 48 hours, is placed in room temperature, fully washed with methanol after crystal dissolves, then be rinsed with water methanol, be put into 50 DEG C of baking ovens and dry
To constant weight, super large pore polymer material is obtained；
The volume ratio of the divinylbenzene monomer and solvent is 20:80~5:95；
The mass ratio of the initiator and divinylbenzene monomer is 0.02:1；
The initiator is redox initiation system；
The solvent is dimethyl sulfoxide (DMSO), and crystal is pore-foaming agent；
The freezing polymerization temperature is less than the fusing point of dimethyl sulfoxide (DMSO).
It is divinylbenzene 80 according to currently preferred, described monomer.
It is 5 according to the volume ratio of currently preferred, described monomer and solvent:95.
Polymer produced by the present invention have super large pore structure, aperture be mainly distributed on 5 ~ 100 nm and
Between 20 ~ 200 μm, resulting polymers have adsorption capacity height, the fast feature of the rate of adsorption, the absorption to crude oil
Amount can reach 32.9 g/g.
Most preferred according to the present invention, a kind of preparation method of super large pore polymer material, steps are as follows：
It takes the divinylbenzene of 0.5 ml to be added in the dimethyl sulfoxide (DMSO) of 9.5 ml, sequentially adds 4.8 μ l N, N- diformazans
Base aniline and 9.2 mg benzoyl peroxides shake mixing, after leading to nitrogen 5 min removing oxygen, go in syringe, seal,
It is freezed 24 hours at -18 DEG C, goes at 4 DEG C and react 48 hours, be placed in room temperature, fully washed with methanol after crystal dissolves
It washs, then is rinsed with water methanol, be put into 50 DEG C of baking ovens and dry to constant weight, obtain super large pore polymer material.
The present invention obtains super large pore polymer material by the method that cryogenic freezing polymerize, can be by changing organic solvent
Addition carry out adjustment apertures rate, to adjust oil absorption.
The present invention uses solvent crystal pore, and preparation method is simple and reliable, and post-processing is simple, and the polymer of gained, which has, to be surpassed
Macroporous structure, pore diameter range are mainly distributed between 5 ~ 100 nm and 20 ~ 200 μm, have adsorption capacity height, the rate of adsorption
Fast feature, polymer can reach 32.9 g/g to the adsorbance of crude oil.
Specific implementation mode
Below by embodiment, the present invention will be further described.The divinylbenzene monomer used in embodiment is divinyl
Benzene 80（Trade name indicates that the content of divinylbenzene is 80%, vinyl ethylbenzene 20%）, Aladdin reagent（China）Co., Ltd produces
Product.
Embodiment 1
It takes the divinylbenzene of 2 ml to be added in the dimethyl sulfoxide (DMSO) of 8 ml, sequentially adds 19.2 μ l N, N- dimethyl benzenes
Amine and 36.8 mg benzoyl peroxides shake mixing, after leading to nitrogen 5 min removing oxygen, go in syringe, seal ,-
It is freezed 24 hours at 18 DEG C, goes at 4 DEG C and react 48 hours, be placed in room temperature, fully washed with methanol after crystal dissolves, then
It is rinsed with water methanol, is put into 50 DEG C of baking ovens and dries to constant weight, obtain super large pore polymer material.
Under room temperature, the polymer material for weighing certain mass is put into and fills the small of 40 g simulated seawaters and 5 g crude oil
In beaker, take out material after adsorbing 1 h, wipe surface oil slick, weigh, calculate polymer is 11.1 to the adsorbance of crude oil
g/g。
Embodiment 2
It takes the divinylbenzene of 1 ml to be added in the dimethyl sulfoxide (DMSO) of 9 ml, sequentially adds 9.5 μ l N, N- dimethyl benzenes
Amine and 18.3 mg benzoyl peroxides shake mixing, after leading to nitrogen 5 min removing oxygen, go in syringe, seal ,-
It is freezed 24 hours at 18 DEG C, goes at 4 DEG C and react 48 hours, be placed in room temperature, fully washed with methanol after crystal dissolves, then
It is rinsed with water methanol, is put into 50 DEG C of baking ovens and dries to constant weight, obtain super large pore polymer material.
Under room temperature, the polymer material for weighing certain mass is put into and fills the small of 40 g simulated seawaters and 5 g crude oil
In beaker, take out material after adsorbing 1 h, wipe surface oil slick, weigh, calculate polymer is 20.9 to the adsorbance of crude oil
g/g。
Embodiment 3
It takes the divinylbenzene of 0.5 ml to be added in the dimethyl sulfoxide (DMSO) of 9.5 ml, sequentially adds 4.8 μ l N, N- diformazans
Base aniline and 9.2 mg benzoyl peroxides shake mixing, after leading to nitrogen 5 min removing oxygen, go in syringe, seal,
It is freezed 24 hours at -18 DEG C, goes at 4 DEG C and react 48 hours, be placed in room temperature, fully washed with methanol after crystal dissolves
It washs, then is rinsed with water methanol, be put into 50 DEG C of baking ovens and dry to constant weight, obtain super large pore polymer material.
Under room temperature, the polymer material for weighing certain mass is put into and fills the small of 40 g simulated seawaters and 5 g crude oil
In beaker, take out material after adsorbing 1 h, wipe surface oil slick, weigh, calculate polymer is 32.9 to the adsorbance of crude oil
g/g。
Claims (2)
1. a kind of preparation method of super large pore polymer material, which is characterized in that steps are as follows：
It takes a certain amount of monomer to be dissolved in solvent, sequentially adds n,N-Dimethylaniline and benzoyl peroxide, shake mixing, lead to
It after nitrogen 5min removes oxygen, goes in syringe, seals, freezed 24 hours at -18 DEG C, go at 4 DEG C and react 48 hours,
It is placed in room temperature, is fully washed with methanol after crystal melting, then be rinsed with water methanol, is put into 50 DEG C of baking ovens that drying to constant weight,
Obtain super large pore polymer material；
The monomer is divinylbenzene；
The solvent is dimethyl sulfoxide (DMSO), and crystal is pore-foaming agent；
The volume ratio of the monomer and solvent is 20:80~5:95；
Polymer material prepared by the method has super large pore structure, and aperture is mainly distributed on 5~100nm and 20~200 μ
Between m.
2. the preparation method of super large pore polymer material as described in claim 1, which is characterized in that steps are as follows：
Take the divinylbenzene of 0.5ml to be added in the dimethyl sulfoxide (DMSO) of 9.5ml, sequentially add 4.8 μ l n,N-Dimethylaniline and
9.2mg benzoyl peroxides vibrate mixing, after leading to nitrogen 5min removing oxygen, go in syringe, seal, cold at -18 DEG C
Freeze 24 hours, goes at 4 DEG C and react 48 hours, be placed in room temperature, fully washed with methanol after crystal melting, then be rinsed with water first
Alcohol, is put into 50 DEG C of baking ovens that drying to constant weight, obtains super large pore polymer material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610816150.9A CN106432563B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of super large pore polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610816150.9A CN106432563B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of super large pore polymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106432563A CN106432563A (en) | 2017-02-22 |
| CN106432563B true CN106432563B (en) | 2018-08-14 |
Family
ID=58167793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610816150.9A Expired - Fee Related CN106432563B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of super large pore polymer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106432563B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602744B (en) * | 2017-03-08 | 2019-09-27 | 济南大学 | A kind of superhigh cross-linking microporous polymer and preparation method thereof |
| CN113234252B (en) * | 2021-06-07 | 2022-08-26 | 石河子大学 | Composite pore crystal glue medium and preparation method thereof |
| CN113533593A (en) * | 2021-06-28 | 2021-10-22 | 济南大学 | Separation analysis method for complex oil-water emulsion system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2070901C1 (en) * | 1992-08-28 | 1996-12-27 | Институт пищевых веществ РАН | Process for preparing polyvinyl alcohol gel |
| CN101845226A (en) * | 2010-04-15 | 2010-09-29 | 四川大学 | Dialdehyde carboxymethyl cellulose-collagen frozen gel and preparation method thereof |
-
2016
- 2016-09-12 CN CN201610816150.9A patent/CN106432563B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2070901C1 (en) * | 1992-08-28 | 1996-12-27 | Институт пищевых веществ РАН | Process for preparing polyvinyl alcohol gel |
| CN101845226A (en) * | 2010-04-15 | 2010-09-29 | 四川大学 | Dialdehyde carboxymethyl cellulose-collagen frozen gel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis of Hydrophobic Polymeric Cryogels with Supermacroporous Structure";Xilu Chen et al.,;《Macromolecular Materials and Engineering》;20160630;第301卷(第6期);第659-664页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106432563A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Novel approach for attapulgite/poly (acrylic acid)(ATP/PAA) nanocomposite microgels as selective adsorbent for Pb (II) ion | |
| CN106432563B (en) | A kind of preparation method of super large pore polymer material | |
| Zhang et al. | Ethylene glycol dimethacrylate modified hyper-cross-linked resins: Porogen effect on pore structure and adsorption performance | |
| Moghbeli et al. | Nanosilica reinforced ion-exchange polyHIPE type membrane for removal of nickel ions: Preparation, characterization and adsorption studies | |
| CN102532375B (en) | Polyacrylamide microsphere | |
| Wu et al. | Polymerization-induced phase separation for the fabrication of magnetic sponges for oil spill reclamation | |
| US5130343A (en) | Process for producing uniform macroporous polymer beads | |
| Jiang et al. | Magnetic ATP/FA/Poly (AA-co-AM) ternary nanocomposite microgel as selective adsorbent for removal of heavy metals from wastewater | |
| CN105273187B (en) | Elastic conduction macromolecule hydrogel, sponge and its preparation method and application | |
| CN106397652B (en) | A method of preparing super big hole high-specific surface polymer | |
| CN104530311B (en) | Tough hydrogel of a kind of breach insensitivity and preparation method thereof | |
| CN102617769A (en) | Nanometer composite porous gel microsphere and preparation method thereof | |
| BRPI0718499A2 (en) | EXPANDABLE POLYSTYRENIC RESIN PARTICULES AND PROCESS FOR THEIR PRODUCTION, PRE-EXPANDED PARTICULES AND MOLDED FOAM PRODUCT | |
| Azhar et al. | A cationic fluorosurfactant for fabrication of high-performance fluoropolymer foams with controllable morphology | |
| CN103159894A (en) | Super-hydrophobic micropore conjugated polymer and strong-hydrophobic sponge adsorbing materials and preparation thereof | |
| CN104841388A (en) | Preparation method for resin adsorbent compounded with mussel shell powder | |
| CN107442081A (en) | The method that porous heavy metal absorbent is constructed using Pickering water base foams as template | |
| CN107837795A (en) | A kind of resin sorbent and preparation method of the load of microorganisms type of degradable greasy dirt | |
| CN105254818A (en) | High-oil-absorption resin and preparation method thereof | |
| CN110935199B (en) | Organosilicon foam with interpenetrating network pH responsiveness | |
| CN107262057A (en) | A kind of preparation method of bilirubin resin anion (R.A.) adsorbent | |
| Jurjevec et al. | Highly porous polyelectrolyte beads through multiple-emulsion-templating: Synthesis and organic solvent drying efficiency | |
| Kekevi et al. | Preparation of hypercrosslinked PolyHIPEs by using a bio-derived monomer | |
| CN112844338B (en) | Black talc-polyvinyl formal gel composite adsorption material | |
| CN107619495A (en) | A kind of preparation method of microballoon accumulation type polystyrene porous material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180814 Termination date: 20200912 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |