CN106188367B - A kind of preparation method of conductive absorption resin - Google Patents

A kind of preparation method of conductive absorption resin Download PDF

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CN106188367B
CN106188367B CN201511001479.1A CN201511001479A CN106188367B CN 106188367 B CN106188367 B CN 106188367B CN 201511001479 A CN201511001479 A CN 201511001479A CN 106188367 B CN106188367 B CN 106188367B
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carbon nanotube
absorption resin
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conductive absorption
reactant
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CN106188367A (en
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高冠道
丁杰
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Nankai University
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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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The carbon nanotube (CNTs) after comprehensive modify is incorporated into using SDEB styrene diethylenebenzene as the method for monomer and then generation polymerisation generation electroconductive resin using situ aggregation method the present invention relates to a kind of.The mass percent that the carbon nanotube accounts for monomer is 0.1% ~ 15%.It is monomer, divinylbenzene for crosslinking agent that preparation method, which is using styrene, toluene makees pore-foaming agent, and azodiisobutyronitrile or dibenzoyl peroxide make initiator, and polyvinyl alcohol etc. makees dispersant, the carbon nanotube of different proportion is added in situ in suspension polymerization, obtains a kind of conductive absorption resin.The electroconductive resin can be used for adsorbing, electric desorption field, can have a wide range of applications in application field of water treatment to avoid a large amount of soda acids or organic solvent needed for conventional resins adsorption/desorption technique are used.

Description

A kind of preparation method of conductive absorption resin
Technical field
The present invention relates to a kind of preparation methods of conductive absorption resin, are in particular a kind of height of incorporation carbon nanotube Molecular Adsorption resin and preparation method thereof.
Technical background
In recent years, macroporous absorbent resin and ion exchange resin are applied to water by countries in the world scientist and researchers Body decolourizes and removal toxic organic pollutant aspect, and achieves significant application effect.Macromolecule resin is set to be led in water process Domain occupies the status that can be despised.But making constant progress with the mankind, absorption resin itself there are the shortcomings that also increasingly It is prominent：Such as need a large amount of organic reagents or soda acid as desorbing agent.And carbon nanotube is with its abundant nanoaperture structure, it is huge Big specific surface area and excellent electric conductivity make it the adsorbent and electrode material being concerned in recent years, but with The extensive use of carbon nanotube and the constantly improve of technology of preparing, carbon nanotube recycling existing for pulverulence is more difficult, It is thus easy to cause a large amount of carbon nanotube can be discharged into environment, immeasurable potential hazard is brought to environment.Therefore it finds One kind can change resin regeneration mode and effectively avoid the release of carbon nanotube in the environment, have for environmental protection It is of great significance.For this purpose, the present invention is directed to which the two to be effectively combined, reaches and complete to be desorbed using electric field action Process.
The research of conductive polymer composites starts from the sixties in last century in the world, and is realized in the mid-1970s Industrialized production and application, only in the demand of U.S.'s conductive polymer composites with the rate delivery of the annual % of 20 %~30 Increase, just there is family more than 200 in the research institution being engaged in this respect.The filler for preparing conductive polymer composite is mainly carbon black, stone Ink, carbon fiber also become the research hotspot of research field, mainly using new carbon as the composite conducting material of additive at present It is compound etc. including conducting polymer and graphene, single wall carbon nanotube and multi-walled carbon nanotube.At present rarely have both at home and abroad about The preparation difficult point of the research of conduction absorption resin, conduction absorption resin is evenly dispersed and carbon of the carbon nanotube in oil phase How to ensure that stablizing for polymerisation carries out under nanotube existence condition.
Invention content
1. technical problems to be solved by the inivention
The present invention provides a kind of preparation method of conductive absorption resin, using simple and practicable method to carbon nanotube into Row pretreatment, enhances its lipophile, so that it is easy in oil phase evenly dispersed；Conductive absorption tree is prepared using situ aggregation method Fat regulates and controls it and synthesizes details so that the synthesis of conduction absorption resin is achieved；
2. technical solution
A kind of conductive absorption resin, is made of carbon nanotube and polystyrene, it is characterised in that：Carbon nanotube is in resin bone Shared mass percent is the % of 0.1 %~15 in frame, and the average grain diameter of resin is 30~100 mesh；
Its step of the preparation method of conductive absorption resin of the present invention is：
(a) modification of carbon nanotube, by carbon nanotube (COOH contents：1~10%, length：2~100um, internal diameter：2~30 Nm 10 min of ultrasound in ethyl alcohol sodium water solution) are placed in, after rear 5~20 min of addition functionalized reagent ultrasound, water at 20~45 DEG C Bath 1 ~ 4h of stirring, suction filtration wash away residual solvent, are dried for standby at 40 DEG C ~ 70 DEG C；
Carbon nanotube in step (a)：Sodium ethoxide：P-chloromethyl styrene=1:0.2~1:1~10；
(b) water phase is configured, is added in water phase and accounts for 0.5 ~ 3% dispersant of water phase quality and 2 ~ 10% salt；
Dispersant and salt used by step (b) water phase are polyvinyl alcohol and sodium chloride respectively；
(c) oil phase is configured, oil phase is made of the carbon nanotube after reactant, pore-foaming agent, initiator and modification, carbon nanotube It is placed in 5 ~ 50 min of ultrasonic disperse in pore-foaming agent, initiator, stirring and dissolving is added after 5 ~ 30min of reactant ultrasonic disperse is added；
Reactant is made of monomer and crosslinking agent two parts in step (c), monomer, crosslinking agent, pore-foaming agent, initiator difference Refer to styrene, divinylbenzene, toluene and azodiisobutyronitrile or dibenzoyl peroxide；
Monomer in step (c)：Crosslinking agent（Mass ratio）=1:0.6~1.2；
Reactant in step (c)：Pore-foaming agent：Initiator（Mass ratio）=1:0.5~4:0.01~0.04；
Reactant in step (c)：Carbon nanotube（Mass ratio）=1:0.001~0.15；
Step (b) and water phase in (c)：Oil phase（Mass ratio）=1:0.15~0.35；
(d) by water phase be added three-necked flask in, oil bath insulated and stirred at 20 ~ 40 DEG C, be added oil phase, adjust mixing speed to Oil droplet size is suitable, is to slowly warm up to 50 ~ 70 DEG C of 1 ~ 5.5 h of reaction, is continuously heating to 70 ~ 80 DEG C of 2 ~ 5h of reaction, finally heats up To 80 ~ 90 DEG C of 1 ~ 4h of reaction, reaction finishes, and after hot water elution changes ethanol rinse into afterwards several times, petroleum ether extracts 8 h, 45 DEG C Lower 12 h of drying adsorbs resin to get conduction.
Advantageous effect
The present invention provides a kind of preparation methods of conductive absorption resin, use functionalized reagent and are carried out to carbon nanotube Modification, substantially increases its hydrophobicity, realizes the successful preparation of conductive absorption resin, preparation method is simple.This hair Bright obtained conductive absorption resin has good size distribution and absorption property, its electricity using benzoic acid as target contaminant Desorption process also shows preferable effect.
Description of the drawings
Fig. 1 is the electron microscope of conductive absorption resin, and good form, surface smooth even is presented in resin balls in figure.
Fig. 2 is the cross-sectional interior detail view of conductive absorption resin, as we know from the figure carbon nano tube surface and its surrounding cloth Expire styrenic polymer.
Fig. 3 is the Dynamic Adsorption curve of conductive absorption resin para Toluic Acid.3 BV.h of flow velocity-1, initial concentration solution 50 Mg/L, it is illustrated that show that electroconductive resin para Toluic Acid has good adsorption capacity, in terms of original solution concentration 5%, the breakthrough point of resin At 450 mL, reach adsorption saturation, 22.5 mg of Dynamic Adsorption total amount, unit adsorbance 17.44 when flow is 750 mL mg/g。
Fig. 4 is the electric desorption figure after electroconductive resin para Toluic Acid absorption.A concentration of 50 mg/L of benzoic acid original solution, it is illustrated that Be 50 mg/L sodium sulphate be electrolyte under conditions of apply voltage 4V benzoic acid electricity desorption curves.It can be seen that in electricity Under the action of benzoic acid be desorbed completely, and action time is short and concentrate, and maximum value is present in 8mL flow.
Specific implementation mode
Example one
A) configuration of oil phase
0.105g carbon nanotubes are placed in ultrasonic disperse 30min in 15g toluene, styrene and divinylbenzene is added after cooling 0.17 g of dibenzoyl peroxide is added in 15 g of reactant of composition, 10 min of ultrasonic disperse, for use after stirring and dissolving；
B) preparation of conductive absorption resin
The aqueous solution that 90 g contain 1 % polyvinyl alcohol and 5 % sodium chloride, the oil bath at 45 DEG C are added in three-necked flask Stirring heat preservation, is added the oil phase being made of styrene, divinylbenzene, toluene, carbon nanotube and dibenzoyl peroxide, and adjusting is stirred It is suitable to oil droplet size to mix speed, is to slowly warm up to 80 DEG C of 4 h of reaction, continues to be to slowly warm up to 90 DEG C of 3.5 h of reaction.Polymerization It finishes, filters out resin, several times with hot water elution, dried after changing ethanol rinse into, 8 are extracted in Soxhlet extractor with petroleum ether H, dry 12 h adsorb resin to get conduction at 45 DEG C；
For the conductive absorption resin grain size synthesized in this implementation in 50~100 mesh, pore agent content is 1 times of reactant, carbon 0.7 % of pipe content.
Example two
A) modification of carbon nanotube
60mL water and 0.025g sodium ethoxides are added in beaker, 0.20g carbon nanotube ultrasonic disperses are added after stirring and dissolving 10 min, after 0.7 g p-chloromethyl styrenes continuation ultrasound, 20 min are then added, 2 h of stirring in water bath at 40 DEG C is used Vacuum apparatus filters and washes away residual agent with ethyl alcohol, uses distilled water instead and washes away ethyl alcohol, removes and dried in 70 DEG C of baking ovens It is spare；
B) outfit of oil phase
The carbon nanotube after 0.20 g has been modified is added in beaker, 2.5 g toluene ultrasonic disperse, 20 min is added, it is cooling 5 g of reactant being made of styrene and divinylbenzene is added afterwards, two isobutyl of initiator azo is added after 10 min of ultrasonic disperse Nitrile, to get oil phase after stirring and dissolving；
C) preparation of conductive absorption resin
In 250 mL three-necked flasks, the aqueous solution containing 1 % polyvinyl alcohol and 5 % sodium chloride is added, is protected at 40 DEG C The oil phase being made of styrene, divinylbenzene, toluene, azodiisobutyronitrile and carbon nanotube is added in temperature, adjusts stirring to oil droplet Size is suitable, is to slowly warm up to 60 DEG C of 2 h of reaction, continues to be to slowly warm up to react 4 h at 75 DEG C, be finally warming up to 85 DEG C 2 h of lower reaction.Polymerization finishes, and filters out resin, several times with hot water elution, is dried after changing ethanol rinse into, with petroleum ether in Soxhlet 8 h are extracted in extractor, dry 12 h are to get electroconductive resin at 45 DEG C；
The conductive absorption resin grain size of the present embodiment synthesis is 30~50 mesh, and pore agent content is 0.5 times of reactant, carbon 4 % of pipe content.
Example three
A) modification of carbon nanotube
160mL water and 0.10g sodium ethoxides are added in beaker, 0.50g carbon nanotube ultrasonic disperses are added after stirring and dissolving 10 min, after 1.0 g p-chloromethyl styrenes continuation ultrasound, 20 min are then added, 2 h of stirring in water bath at 40 DEG C is used Vacuum apparatus filters and washes away residual agent with ethyl alcohol, uses distilled water instead and washes away ethyl alcohol, removes and dried in 70 DEG C of baking ovens It is spare；
B) outfit of oil phase
The carbon nanotube after 0.50 g has been modified is added in beaker, 20 g toluene ultrasonic disperse, 20 min is added, it is cooling 10 g of reactant being made of styrene and divinylbenzene is added afterwards, two isobutyl of initiator azo is added after 10 min of ultrasonic disperse Nitrile, to get oil phase after stirring and dissolving；
C) preparation of conductive absorption resin
In 250 mL three-necked flasks, the aqueous solution containing 1 % polyvinyl alcohol and 5 % sodium chloride is added, is protected at 40 DEG C The oil phase being made of styrene, divinylbenzene, toluene, azodiisobutyronitrile and carbon nanotube is added in temperature, adjusts stirring to oil droplet Size is suitable, is to slowly warm up to 60 DEG C of 2.5 h of reaction, continues to be to slowly warm up to react 3 h at 75 DEG C, be finally warming up to 85 2.5 h are reacted at DEG C.Polymerization finishes, and filters out resin, several times with hot water elution, dries after changing ethanol rinse into, is existed with petroleum ether 8 h are extracted in Soxhlet extractor, 12 h are dried at 45 DEG C, up to electroconductive resin；
The conductive absorption resin grain size of the present embodiment synthesis is 30~50 mesh, and pore agent content is 2 times of reactant, carbon pipe 5 % of content.

Claims (9)

1. a kind of conductive absorption resin, it is characterised in that utilize carboxyl function group and the corresponding functionalized reagent in carbon nanotube Substitution reaction occurs, substantially increases the hydrophobicity of carbon nanotube, specific preparation method is as follows：
COOH contents are 1~10% by the modification of step 1 carbon nanotube, length：2~100um, internal diameter：The carbon of 2~30nm is received Mitron is placed in ultrasound 10min in ethyl alcohol sodium water solution, after 5~120min of rear addition 1-chloro-4-methyl-benzene ultrasound, at 20~45 DEG C 2~4h of stirring in water bath, suction filtration wash away residual solvent, are dried for standby at 40 DEG C~70 DEG C；
Step 2 configures water phase, and 0.5~3% dispersant and 2~10% salt are added in water phase；
Step 3 configures oil phase, and oil phase is made of the carbon nanotube after reactant, pore-foaming agent, initiator and modification, and carbon nanotube is set Initiator, stirring and dissolving is added after 5~30min of reactant ultrasonic disperse is added in 5~50min of ultrasonic disperse in pore-foaming agent；
Step 4 by water phase be added three-necked flask in, oil bath insulated and stirred at 20~40 DEG C, be added oil phase, adjust mixing speed to Oil droplet size is suitable, is to slowly warm up to 50~70 DEG C of 1~5.5h of reaction, is continuously heating to 70~80 DEG C of 2~5h of reaction, finally rises To 85~90 DEG C of 1~4h of reaction, reaction finishes temperature, and after hot water elution changes ethanol rinse into afterwards several times, petroleum ether extracts 8h, 45 DEG C Lower dry 12h adsorbs resin to get conduction.
2. a kind of conductive absorption resin according to claim 1, it is characterised in that：Carbon nanotube accounts for SDEB styrene diethylenebenzene The mass percent of the reactant of composition is 0.1%~15%.
3. the preparation method of conductive absorption resin according to claim 1, it is characterised in that：Carbon nanotube in step 1：Second Sodium alkoxide：Mass ratio=1 of dressing agent:0.2~1:1~10.
4. a kind of conductive absorption resin according to claim 1, it is characterised in that：Dispersant in step 2 and salt difference It is polyvinyl alcohol and sodium chloride.
5. a kind of conductive absorption resin according to claim 1, it is characterised in that：Reactant is by monomer and friendship in step 3 Join agent two parts composition, monomer, crosslinking agent, pore-foaming agent, initiator refer respectively to styrene, divinylbenzene, toluene and azo two Isobutyronitrile or dibenzoyl peroxide.
6. a kind of conductive absorption resin according to claim 1, it is characterised in that：Monomer in step 3：The quality of crosslinking agent Than=1:0.6~1.2.
7. a kind of conductive absorption resin according to claim 1, it is characterised in that：Reactant in step 3：Pore-foaming agent：Draw Send out mass ratio=1 of agent:1~4:0.01~0.04.
8. a kind of conductive absorption resin according to claim 1, it is characterised in that：Reactant in step 3：Carbon nanotube matter Measure ratio=1:0.001~0.15.
9. a kind of conductive absorption resin according to claim 1, it is characterised in that：Water phase in step 2 and 3：The matter of oil phase Measure ratio=1:0.15~0.35.
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CN102372812A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Macroporous strong alkaline carbon nanotube composite ion exchange resin and preparation method thereof
CN102372811A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Preparation method of macroporous organic/inorganic nanometer composite resin
CN102702554A (en) * 2012-06-29 2012-10-03 山东轻工业学院 Preparation method of copolymer grafted carbon nano-tube super-hydrophobic material
CN103922307A (en) * 2014-03-31 2014-07-16 北京化工大学 Magnetic carbon nanotube and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN102372812A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Macroporous strong alkaline carbon nanotube composite ion exchange resin and preparation method thereof
CN102372811A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Preparation method of macroporous organic/inorganic nanometer composite resin
CN102702554A (en) * 2012-06-29 2012-10-03 山东轻工业学院 Preparation method of copolymer grafted carbon nano-tube super-hydrophobic material
CN103922307A (en) * 2014-03-31 2014-07-16 北京化工大学 Magnetic carbon nanotube and preparation method thereof

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