CN106084155B - The multistage pore polymer detached for oil water mixture and lotion without method for preparing template - Google Patents

The multistage pore polymer detached for oil water mixture and lotion without method for preparing template Download PDF

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CN106084155B
CN106084155B CN201610592864.6A CN201610592864A CN106084155B CN 106084155 B CN106084155 B CN 106084155B CN 201610592864 A CN201610592864 A CN 201610592864A CN 106084155 B CN106084155 B CN 106084155B
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oil
water
lotion
water mixture
template
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CN106084155A (en
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张招柱
李永
葛博
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • 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
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/045—Breaking emulsions with coalescers
    • 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
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a kind of multistage pore polymers detached for oil water mixture and lotion without method for preparing template, the specific steps are：Divinylbenzene, nano silicon dioxide, azodiisobutyronitrile are added in ethyl acetate and are mixed to form pre-polymerization liquid；Pre-polymerization liquid is reacted under hydrothermal conditions, finally volatilizes solvent.It is characteristic of the invention that ethyl acetate avoids using and post-processing for template not only as solvent but also as pore-foaming agent；A step is realized in polymerization process in situ for hierarchical porous structure, low-surface-energy and multiple dimensioned coarse structure；Resulting materials have high porosity, very high specific surface area, pore volume and excellent super-hydrophobic super-oleophylic.Therefore the material can be not only used for the separation of conventional oil water mixture and can be used for the lotion separation of a plurality of types of oil-in-water types such as nanoscale/submicron order and water-in-oil type.Low in raw material price of the present invention, preparation condition is mild and does not need to complicated equipment, avoids using and removing for template.

Description

The multistage pore polymer detached for oil water mixture and lotion is prepared without template Method
Technical field
The present invention relates to a kind of multistage pore polymers detached for oil water mixture and lotion without method for preparing template, Specifically hierarchical porous structure and super-hydrophobicity are introduced into hydro-thermal polymerization process in polymeric system, so as to obtain that there is height Spend the material of porous structure, high-specific surface area, pore volume and excellent super-hydrophobic super-oleophylic.This multilevel hole material can be applied In water-oil separating especially oil hydrosol separation field.
Background technology
The water pollution accidents mankind of getting worse are rely life caused by being taken place frequently due to a large amount of trade effluents and oil leak event The environment deposited.For environment and the requirement of economic development, there is an urgent need to seek the approach of high-efficiency and economic except the oil in decontaminated water or Person's organic pollution.To solve the problems, such as this, a series of materials such as inorganic adsorbent, activated carbon or natural is utilized in people Fiber and other material adsorb water surface greasy dirt, but due to its not only hydrophilic but also oleophylic thus poor selectivity, affect practical application.
In order to seek the separating pathway of high-efficiency and economic, people are by changing the infiltration sexual development a series of new of material The graphene sponge of water-oil separating material, such as super-hydrophobic/super-oleophilic perforated membrane, superoleophobic/super hydrophilic film and high absorption capacity, The porous integral materials such as the polyurethane sponge of carbon nanotube sponge and modification.These materials have a variety of oil and organic solvent Selective adsorption.But expensive raw material or complicated harsh preparation condition prevent them from preparing on a large scale, and Only effective to the separation of simple oil water mixture, the oil hydrosol above-mentioned material stablized for surfactant just loses its point From function.Even if there are some materials that can be used for lotion separation but can typically be only used to point of Water-In-Oil or oil-in-water single emulsion From the water-oil separating material prepared while can efficiently separate Water-In-Oil and oil-in-water system is relatively difficult.Therefore it prepares It is cheap, it is environmentally protective, and Water-In-Oil can be detached simultaneously and the functional material of oil-in-water emulsion systems is extremely urgent.
It is more to water-oil separating material research in recent years both at home and abroad, but be especially suitable for simultaneously for oil hydrosol separation The material requirements of Water-In-Oil and oil-in-water emulsion systems separation is harsh, therefore at present for simultaneously suitable for Water-In-Oil and oil-in-water The material report of emulsion system separation is few.Tuteja etc. is prepared by the method for dip-coating for Water-In-Oil and oil-in-water emulsion The membrane material of system separation（Nat. Commun.2012, 3, 1025）.Xue Li is new etc., which to prepare PVDF films, realizes Water-In-Oil With the separation of oil-in-water emulsion systems（Adv. Mater. 2014, 26, 2943−2948）, so as to cause the extensive of people Concern.However, related template-free method prepares multistage pore polymer realization Water-In-Oil and oil-in-water emulsion systems point both at home and abroad at present From material be but rarely reported.It is usually required when preparing porous material numerous using freeze-drying or template, special equipment Trivial template preparation process and needs etches or other post processings are to remove the template used, takes costliness, does not meet currently The theory of Green Chemistry, far from meeting its wide application field.In addition, the mechanical performance of material is in use often Practical application cannot be met.Therefore present invention is simple and practicable, the strong multistage pore polymer of stability for Water-In-Oil and The separation of oil-in-water emulsion systems is extremely necessary, has potential great market for the processing aspect of complex wastewater.
Invention content
The purpose of the present invention is to provide a kind of multistage pore polymer detached for oil water mixture and lotion without mould Plate preparation method.
Preparation method green of the present invention is simple, and gained multistage pore polymer can arbitrarily be ground, and have good machine Tool intensity and can be recycled, solve filtering type be demulsified nethike embrane when being used for multiple times because lotion is blocking microporous, pollution nethike embrane And the problem of separative efficiency is caused to substantially reduce, so as to effectively extend the service life of material.
Technical scheme of the present invention：Use of the suitable solvent as pore-foaming agent to avoid template is selected, is gathered by hydro-thermal The method of conjunction obtains the novel super-hydrophobic water-oil separating material with hierarchical porous structure, high-specific surface area, and obtained material can For the separation of oil water mixture and oil hydrosol.
The multistage pore polymer detached for oil water mixture and lotion without method for preparing template, it is characterised in that including Following steps：
1) by nano silicon dioxide, 10~40 min of ultrasonic disperse is up to silica dispersions in ethyl acetate, then Monomer divinylbenzene, initiator azodiisobutyronitrile are added in into silica under the conditions of rotating speed is 500~1300 r/min 2~6 h are stirred in dispersion liquid up to pre-polymerization liquid；
2) by above-mentioned pre-polymerization liquid in 60~150 DEG C of 12~24 h of hydro-thermal reaction, reaction gained mixture is cooled to room temperature After place it in 20~50 DEG C of volatilizations until solvent volatilization is complete, then grind up to for oil water mixture and oil hydrosol point From multistage pore polymer.
The mass percent of the nano silicon dioxide and divinylbenzene is 4.0~16.0%；The azodiisobutyronitrile Mass percent with divinylbenzene is 1.6~4.0%；The mass volume ratio of the divinylbenzene and ethyl acetate is 0.05~0.1 g/mL.
Compared with prior art, the advantage of the invention is that：
1) preparation process is simple, and the advantages of porous material and super hydrophobic material is combined, and passes through a step hydro-thermal Method is obtained not only with hierarchical porous structure and high-specific surface area but also with the water-oil separating material of excellent super-hydrophobicity.
2) preparation process only needs solvent flashing to can obtain hierarchical porous structure, avoids the cumbersome mould of template without template The processes such as plate preparation and removing.The raw material used is floride-free and solvent low toxicity is environmentally friendly, meets the theory of current Green Chemistry.
3) material can be used not only for the separation of simple oil water mixture, and can detach nanoscale/submicron order It is detached etc. the lotion of a plurality of types of water-in-oil types and oil-in-water type, has greatly expanded the scope of application of material.
4) the good mechanical stability of the material arbitrarily can grind and accumulate, and can reuse, and solve filtering type Be demulsified nethike embrane when being used for multiple times because lotion is blocking microporous, pollution nethike embrane due to separative efficiency is caused to substantially reduce the problem of.
Description of the drawings
Fig. 1 is the picture of the made product of the embodiment of the present invention 1.
Fig. 2 is that the made product of the embodiment of the present invention 2 is used for toluene Bao Shui and water armored benzole soln separating effect figure.
Specific embodiment
Embodiment 1：
0.1 gram of silica
2.5 grams of divinylbenzene
30 mL of ethyl acetate
0.07 gram of azodiisobutyronitrile
120 DEG C of hydrothermal temperature
18 h of reaction time
25 DEG C of solvent volatilization temperature
Each component is weighed according to the above ratio, and nano silicon dioxide is distributed in solvent first, ultrasonic time is 10 min, Then monomer divinylbenzene, initiator azodiisobutyronitrile are added under the conditions of in rotating speed for 800 r/min above-mentioned mixed It closes and 2 h is stirred in object, form pre-polymerization liquid.Then above-mentioned pre-polymerization liquid is transferred in the polytetrafluoroethyllining lining of 100 mL, with 5 DEG C/min heating rates rise to 120 DEG C of 18 h of hydro-thermal reaction.It is cooled to room temperature and waves solvent after reaction in 25 DEG C of environment Distribute the full hydrophobic polymer integral material that can obtain multi-stage porous.It is the specific surface area more than 160 ° that it, which measures its contact angle, In 800 m2/ g or so.Being seated in after being ground in chromatographic column can separation of methylbenzene packet aqueous emulsion, chloroform packet aqueous emulsion and right The oil-in-water emulsion answered.
Embodiment 2：
0.2 gram of silica
2.5 grams of divinylbenzene
32 mL of ethyl acetate
0.07 gram of azodiisobutyronitrile
110 DEG C of hydrothermal temperature
20 h of reaction time
30 DEG C of solvent volatilization temperature
Each component is weighed according to the above ratio, and nano silicon dioxide is distributed in solvent first, ultrasonic time is 20 min, Then monomer divinylbenzene, initiator azodiisobutyronitrile are added under the conditions of in rotating speed for 1000 r/min above-mentioned mixed It closes and 3 h is stirred in object, form pre-polymerization liquid.Then above-mentioned pre-polymerization liquid is transferred in the polytetrafluoroethyllining lining of 100 mL, with 5 DEG C/min heating rates rise to 110 DEG C of 20 h of hydro-thermal reaction.It is cooled to room temperature and waves solvent after reaction in 30 DEG C of environment Distribute the full hydrophobic polymer integral material that can obtain multi-stage porous.It is the specific surface area more than 160 ° that it, which measures its contact angle, More than 820 m2/g.Being seated in after being ground in chromatographic column can separation of methylbenzene packet aqueous emulsion, chloroform packet aqueous emulsion and correspondence Oil-in-water emulsion.
Embodiment 3：
0.4 gram of silica
6.0 grams of divinylbenzene
80 mL of ethyl acetate
0.15 gram of azodiisobutyronitrile
110 DEG C of hydrothermal temperature
24 h of reaction time
30-40 DEG C of solvent volatilization temperature
Each component is weighed according to the above ratio, and nano silicon dioxide is distributed in solvent first, ultrasonic time is 20 min, Then monomer divinylbenzene, initiator azodiisobutyronitrile are entered to above-mentioned mixing under the conditions of in rotating speed for 1000 r/min 5 h are stirred in object, form pre-polymerization liquid.Then above-mentioned pre-polymerization liquid is transferred in the polytetrafluoroethyllining lining of 200 mL, with 5 DEG C/ Min heating rates rise to 110 DEG C of 24 h of hydro-thermal reaction.It is cooled to room temperature and waves solvent after reaction in 30-40 DEG C of environment Distribute the full hydrophobic polymer integral material that can obtain multi-stage porous.It is the specific surface area more than 160 ° that it, which measures its contact angle, More than 800 m2/g.Being seated in after being ground in chromatographic column can separation of methylbenzene packet aqueous emulsion, chloroform packet aqueous emulsion and correspondence Oil-in-water emulsion.

Claims (1)

1. the multistage pore polymer detached for oil water mixture and lotion without method for preparing template, it is characterised in that including with Lower step：
1) by nano silicon dioxide, 10~40 min of ultrasonic disperse up to silica dispersions, is then turning in ethyl acetate Monomer divinylbenzene, initiator azodiisobutyronitrile is are added in silica dispersion by speed under the conditions of 500~1300 r/min 2~6 h are stirred in liquid up to pre-polymerization liquid；
2) by above-mentioned pre-polymerization liquid in 60~150 DEG C of 12~24 h of hydro-thermal reaction, will reaction gained mixture be cooled to room temperature after will It is placed in 20~50 DEG C of volatilizations until solvent volatilization, then grinds to detach for oil water mixture and oil hydrosol completely Multistage pore polymer；
The mass percent of the nano silicon dioxide and divinylbenzene is 4.0~16.0%；The azodiisobutyronitrile and two The mass percent of vinyl benzene is 1.6~4.0%；The mass volume ratio of the divinylbenzene and ethyl acetate for 0.05~ 0.1 g/mL。
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CN107474190B (en) * 2017-08-09 2019-09-13 中国科学院新疆理化技术研究所 A kind of biology base coagulates the preparation method and application of light wood material
CN110760030B (en) * 2019-11-05 2021-06-29 江苏慧智新材料科技有限公司 Preparation method and application of hydrophobic material based on nanoparticles
CN114471486A (en) * 2022-01-29 2022-05-13 蚌埠学院 Super-hydrophobic silicon dioxide/polydivinylbenzene nano composite material and preparation method thereof

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