CN104689797A - Self-crosslinking polymeric oil-absorption material and preparation method thereof - Google Patents
Self-crosslinking polymeric oil-absorption material and preparation method thereof Download PDFInfo
- Publication number
- CN104689797A CN104689797A CN201310654864.0A CN201310654864A CN104689797A CN 104689797 A CN104689797 A CN 104689797A CN 201310654864 A CN201310654864 A CN 201310654864A CN 104689797 A CN104689797 A CN 104689797A
- Authority
- CN
- China
- Prior art keywords
- self
- absorption material
- polyurethane foam
- ferric trichloride
- oil absorption
- 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.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a self-crosslinking polymeric oil-absorption material and a preparation method thereof. The method is characterized by comprising the following steps: with benzyl bichloride and 2,6-bischloromethyl-naphthalene as polymeric monomers, polyurethane foam particles as an auxiliary material, 1,2-dichloroethane as a solvent and ferric trichloride as a catalyst, carrying out nitrogen-protected reaction for 5 hours under the conditions of reflux and agitation at 65 to 85 DEG C, wherein the mass ratio of benzyl bichloride to 2,6-bischloromethyl-naphthalene is 2: 8 to 8: 2, the mass ratio of the polymeric monomers to the polyurethane foam particles is 2: 1 to 20: 1, the mass ratio of the polymeric monomers to ferric trichloride is 1: 0.5 to 1: 1.5, and the mass ratio of the polymeric monomers to 1,2-dichloroethane is 1: 10 to 1: 40; then filtering reaction products, then repeatedly washing the filtered matters with water and ethanol until a filtrate is clear; and finally, carrying out washing with ether and drying so as to obtain the self-crosslinking polymeric oil-absorption material. The self-crosslinking polymeric oil-absorption material provided by the invention has high porosity and good adsorption effect on organic matters, and can be applied to the fields of spilled oil recovery and adsorption of organic matters in water.
Description
Technical field
The present invention is a kind of self-crosslinking polymer oil absorption material and preparation method thereof, relates to technical field of petroleum industry.
Background technology
In recent years, day by day frequent along with the develop rapidly of domestic petroleum plumbing installations and offshore oil exploitation activity and oil transportation at sea, oil accident happens occasionally.No matter be marine oil overflow or land oil spilling, oils is once leak, all can cause harm difficult to the appraisal to natural environment, aquaculture, shallow water seashore, harbour industry, earth's surface and underground water source, surface vegetation etc., Oil spills is called as the super killer of marine environment.The pollution of land water body, also serious harm can be caused to environment, the impact that such as Song Hua River in 2005 is exploded by chemical plant, benzene class material enters river, along with the flowing of water body, pollutant drifts about to downstream, causes Heilungkiang, Song Hua River section to be subject to severe contamination, and two sides ecology, aquatic products and DRINKING WATER suffer lethal challenge.In addition, along with the development of society, the progress of science and technology, a large amount of industrial wastewaters of annual generation, such as: the industrial wastewaters such as electroplating wastewater, wastewater from chemical industry, dyeing waste water, containing a large amount of organic murder by poisoning things in these industrial wastewaters, how to separate fast from these industrial wastewaters from organic harmful toxic matter, thus reduce industrial wastewater to the pollution of environment, be the difficult problem be not yet solved always.
Porous polymer oil absorption material is a kind of high molecular polymer with three-dimensional netted chemical crosslinking structure, compared with traditional oil absorption material, porous polymer oil absorption material has that porosity organism kinds that is large, that can adsorb is many, adsorbance is large, adsorption rate is fast, oil-water selectivity high.The synthon of current high score subclass oil absorption material is mainly esters of acrylic acid and alpha-olefines, because the latter is expensive, therefore mostly adopts acrylic ester monomer to synthesize.Synthetic method mainly adopts suspension polymerisation and emulsion polymerisation, take esters of acrylic acid as raw material, and oleosoluble radical initiators is that initator carries out initiated polymerization.Chinese patent CN1095727 discloses a kind of synthetic method of oil absorption material, with acrylic acid, esters of acrylic acid material for monomer, with N, N-di-2-ethylhexylphosphine oxide acrylamide, EDIA class are crosslinking agent, with gelatin, polyvinyl alcohol, cellulose, inorganic salts powder for dispersant, calcium dodecyl benzene sulfonate is dispersion aids, has prepared oil absorption material by free radical suspensioning polymerization.People (the Shandong Sunyu such as Shandong Sunyu, Lu Jianmei, Nanjing Chemical Engineering College's journal, 1995,2,43-47) with acrylic acid-2-ethyl caproite and butyl methacrylate for monomer, in atent solvent, carry out suspension polymerisation, react the solvent that terminates in rear methanol extraction particle thus prepared porous granule shape sorbing material.These methods need specific means to remove the pore-foaming agent added in preparation process, and preparation process is complicated, and cost is higher, is unfavorable for the industry amplification of product and applying of product.
Summary of the invention
The object of the invention is to invent self-crosslinking polymer oil absorption material that a kind of porosity is large, oil absorbing effect good, speed of oil absorption is fast and preparation method thereof, it belongs to the one of porous polymer materials.
A kind of self-crosslinking polymer oil absorption material and preparation method thereof, it is characterized in that with xylylene dichlorides and 2, 6-dichloromethyl naphthalene is polymerization single polymerization monomer, polyurethane foam particle is auxiliary material, 1, 2-dichloroethanes is solvent, ferric trichloride is catalyst, react 4 ~ 6 hours under the condition of 65 ~ 85 DEG C of return stirrings with nitrogen protection, after product is filtered, repeatedly use water, the washed screening of ethanol is until filtered fluid is limpid, finally use washed with diethylether, self-crosslinking polymer oil absorption material can be obtained after drying, wherein the percentage by weight of polymerization single polymerization monomer xylylene dichlorides is 0.4 ~ 6.93%, polymerization single polymerization monomer 2, 6-dichloromethyl naphthalene is 0.4 ~ 6.93%, polyurethane foam particle is 0.43 ~ 1.16%, ferric trichloride is 3.49 ~ 4.33%, 1, 2-dichloroethanes is 86.6 ~ 93%.
Concrete implementation step is as follows:
1) in the reactor of agitating device, 1 is added successively, 2-dichloroethanes, xylylene dichlorides, 2,6-dichloromethyl naphthalene, polyurethane foam particle, with the air in high pure nitrogen fully displacement system, and uniform stirring, wherein the percentage by weight of polymerization single polymerization monomer xylylene dichlorides is 0.4 ~ 6.93%, polymerization single polymerization monomer 2,6-dichloromethyl naphthalene is 0.4 ~ 6.93%, and polyurethane foam particle is 0.43 ~ 1.16%, 1,2-dichloroethanes is 86.6 ~ 93%;
2) in the protection downhill reaction still of high pure nitrogen, add catalyst ferric trichloride, under the condition of return stirring, be progressively warming up to 65 ~ 85 DEG C of reactions 4 ~ 6 hours, the mass percent of catalyst ferric trichloride is 3.49 ~ 4.33%;
3), after product being filtered, repeatedly use the washed screening of water, ethanol until filtered fluid is limpid, finally use washed with diethylether, after drying, self-crosslinking polymer oil absorption material can be obtained.
The self-crosslinking polymer oil absorption material porosity that the present invention is prepared by one-step method is large, specific area is high, and BET specific surface area is greater than 1500m
2/ g, and can adjust by regulating polymerization single polymerization monomer ratio.Good adsorption effect is all had for product oil, lightweight low viscosity crude oil and small organic molecule (such as: benzene, aniline, nitrobenzene, phenol, Methyl Benzene-o-dicarboxylate etc.).This self-crosslinking polymer oil absorption material production technology is simple, course of reaction is easy to control, can effectively in adsorbed water or land oil spilling.In addition, Organic substance in water absorption industry can also be applied in, have broad application prospects in petroleum industry field and water treatment field.
Detailed description of the invention
Embodiment 1.
Take 100g1 successively; 2-dichloroethanes, 2g xylylene dichlorides, 8g2; 6-dichloromethyl naphthalene adds in the reactor of band agitating device; then electric mixer uniform stirring is started; with the air in high pure nitrogen fully displacement system; 5g ferric trichloride is added under nitrogen protection again in there-necked flask; slowly be warming up to 80 DEG C of reactions 5 hours; after product is filtered; repeatedly use the washed screening of water, ethanol until filtered fluid is limpid; finally use washed with diethylether, after drying, self-crosslinking polymer oil absorption material can be obtained.
Through test, the BET specific surface area of this porous polymer oil suction particle is 1560m
2/ g is 15 times to the absorption multiplying power of kerosene, and the absorption multiplying power of p-nitrophenyl is 31 times.
Embodiment 2.
Take 100g1 successively; 2-dichloroethanes, 8g xylylene dichlorides, 2g2; 6-dichloromethyl naphthalene adds in the reactor of band agitating device; then electric mixer uniform stirring is started; with the air in high pure nitrogen fully displacement system; 5g ferric trichloride is added under nitrogen protection again in there-necked flask; slowly be warming up to 80 DEG C of reactions 5 hours; after product is filtered; repeatedly use the washed screening of water, ethanol until filtered fluid is limpid; finally use washed with diethylether, after drying, self-crosslinking polymer oil absorption material can be obtained.
Through test, the BET specific surface area of this porous polymer oil suction particle is 2430m
2/ g is 20 times to the absorption multiplying power of kerosene, and the absorption multiplying power of p-nitrophenyl is 40 times.
Claims (2)
1. a self-crosslinking polymer oil absorption material, it is characterized in that with xylylene dichlorides and 2, 6-dichloromethyl naphthalene is polymerization single polymerization monomer, polyurethane foam particle is auxiliary material, 1, 2-dichloroethanes is solvent, ferric trichloride is catalyst, react 4 ~ 6 hours under the condition of 65 ~ 85 DEG C of return stirrings with nitrogen protection, after product is filtered, repeatedly use water, the washed screening of ethanol is until filtered fluid is limpid, finally use washed with diethylether, self-crosslinking polymer oil absorption material can be obtained after drying, wherein the percentage by weight of polymerization single polymerization monomer xylylene dichlorides is 0.4 ~ 6.93%, polymerization single polymerization monomer 2, 6-dichloromethyl naphthalene is 0.4 ~ 6.93%, polyurethane foam particle is 0.43 ~ 1.16%, ferric trichloride is 3.49 ~ 4.33%, 1, 2-dichloroethanes is 86.6 ~ 93%.
2. a preparation method for self-crosslinking polymer oil absorption material as claimed in claim 1, is characterized in that concrete implementation step is as follows:
1) in the reactor of agitating device, 1 is added successively, 2-dichloroethanes, xylylene dichlorides, 2,6-dichloromethyl naphthalene, polyurethane foam particle, with the air in high pure nitrogen fully displacement system, and uniform stirring, wherein the percentage by weight of polymerization single polymerization monomer xylylene dichlorides is 0.4 ~ 6.93%, polymerization single polymerization monomer 2,6-dichloromethyl naphthalene is 0.4 ~ 6.93%, and polyurethane foam particle is 0.43 ~ 1.16%, 1,2-dichloroethanes is 86.6 ~ 93%;
2) in the protection downhill reaction still of high pure nitrogen, add catalyst ferric trichloride, under the condition of return stirring, be progressively warming up to 65 ~ 85 DEG C of reactions 4 ~ 6 hours, the mass percent of catalyst ferric trichloride is 3.49 ~ 4.33%;
3), after product being filtered, repeatedly use the washed screening of water, ethanol until filtered fluid is limpid, finally use washed with diethylether, after drying, self-crosslinking polymer oil absorption material can be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310654864.0A CN104689797B (en) | 2013-12-06 | 2013-12-06 | A kind of self-crosslinking polymer oil absorption material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310654864.0A CN104689797B (en) | 2013-12-06 | 2013-12-06 | A kind of self-crosslinking polymer oil absorption material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104689797A true CN104689797A (en) | 2015-06-10 |
| CN104689797B CN104689797B (en) | 2017-04-05 |
Family
ID=53337568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310654864.0A Active CN104689797B (en) | 2013-12-06 | 2013-12-06 | A kind of self-crosslinking polymer oil absorption material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104689797B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095727A (en) * | 1993-05-27 | 1994-11-30 | 天津理工学院 | Synthetic resin with high oil absorbency |
| CN101575404A (en) * | 2009-06-10 | 2009-11-11 | 北京化工大学 | Method for preparing high oil-absorbing resin containing cyclodextrin molecule |
| KR20110004711A (en) * | 2009-07-08 | 2011-01-14 | 주식회사 엘지화학 | Crosslinked polymer having a oil absorbancy and method of preparing the same |
| CN102553546A (en) * | 2012-01-18 | 2012-07-11 | 中国人民解放军63971部队 | High-molecule adsorption material |
| CN103059252A (en) * | 2013-01-22 | 2013-04-24 | 南京工业大学 | Hydrophobic high oil absorption soft polyurethane foam material and preparation method thereof |
-
2013
- 2013-12-06 CN CN201310654864.0A patent/CN104689797B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095727A (en) * | 1993-05-27 | 1994-11-30 | 天津理工学院 | Synthetic resin with high oil absorbency |
| CN101575404A (en) * | 2009-06-10 | 2009-11-11 | 北京化工大学 | Method for preparing high oil-absorbing resin containing cyclodextrin molecule |
| KR20110004711A (en) * | 2009-07-08 | 2011-01-14 | 주식회사 엘지화학 | Crosslinked polymer having a oil absorbancy and method of preparing the same |
| CN102553546A (en) * | 2012-01-18 | 2012-07-11 | 中国人民解放军63971部队 | High-molecule adsorption material |
| CN103059252A (en) * | 2013-01-22 | 2013-04-24 | 南京工业大学 | Hydrophobic high oil absorption soft polyurethane foam material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BUYI LI ET AL: "A New Strategy to Microporous Polymers: Knitting Rigid Aromatic Building Blocks by External Cross-Linke", 《MACROMOLECULES》 * |
| 魏徵 等: "聚氨酯泡沫的制备及吸油性能", 《高分子材料科学与工程》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104689797B (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104341546B (en) | A kind of preparation method of shelly oil absorbing polymer microsphere | |
| Li et al. | Studies on the adsorption of dyes, Methylene blue, Safranin T, and Malachite green onto Polystyrene foam | |
| Hernández-Abreu et al. | Enhanced removal of the endocrine disruptor compound Bisphenol A by adsorption onto green-carbon materials. Effect of real effluents on the adsorption process | |
| Haleem et al. | A systematic review on new advancement and assessment of emerging polymeric cryogels for environmental sustainability and energy production | |
| CN101786751B (en) | Emergency repair process for treating pollution of natural water body emulsified oil | |
| CN101786772A (en) | Efficient biological treatment method for polymer-containing sewage in oil field | |
| CN104056607B (en) | A kind of Enteromorpha gel oil absorption material and preparation method thereof | |
| Liu et al. | Adsorption of Cr (VI) by modified chitosan from heavy-metal polluted water of Xiangjiang River, China | |
| CN103232138B (en) | Combined constructed wetland treatment method and system for nitrobenzene wastewater | |
| Murugesan et al. | Kinetic and thermodynamic studies on the removal of Zn2+ and Ni2+ from their aqueous solution using poly (phenylthiourea) imine | |
| CN105399896A (en) | Preparation method of gel material for adsorbing heavy metal ions and phenolic compound and product of gel material | |
| CN102491494B (en) | Simulator for adsorption and strengthened microbiological degradation of marine spilled oil pollution | |
| CN104927063A (en) | Method for adsorbing and recycling phenolic compounds in industrial wastewater and method for manufacturing adsorption materials | |
| CN102241801B (en) | Acrylic acid(AA)/sodium 2-acrylamide-2-methylpro panesulfonic acid(AMPS-Na)/diisocyanate-modified allyl cyclodextrin (MACD) copolymer | |
| CN103333286B (en) | A kind of oil-absorbing resin and preparation method thereof | |
| CN202358953U (en) | Simulation device for adsorption and microbial enhanced degradation of marine oil spill pollution | |
| CN102489265B (en) | Vegetable sponge used for adsorbing oil pollutants and modified products thereof | |
| Chen et al. | Hydrophobic organogel sorbent and its coated porous substrates for efficient oil/water emulsion separation and effective spilled oil remediation | |
| CN101786712B (en) | Anti-wave emergency restoration process for polluted natural water body | |
| CN202936294U (en) | Novel sludge treatment equipment | |
| CN105664869A (en) | Preparation of lauramidopropyl betaine modified palm tree bark adsorbent | |
| CN106732469A (en) | A kind of preparation method of magnetic absorption dephosphorization agent and its renovation process of product | |
| CN104689797A (en) | Self-crosslinking polymeric oil-absorption material and preparation method thereof | |
| Yang et al. | Preparation of cationic waste paper and its application in poisonous dye removal | |
| CN104628926B (en) | A kind of porous polymer oil suction particle and preparation method thereof |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211105 Address after: Room 08-10, 6 / F, block a, No. 5, Dongtucheng Road, Chaoyang District, Beijing 100013 Patentee after: National Petroleum and natural gas pipeline network Group Co.,Ltd. Address before: 100007 Oil Mansion, 9 North Avenue, Dongcheng District, Beijing, Dongzhimen Patentee before: PETROCHINA Co.,Ltd. |