CN116178606B - Adsorption resin containing metal groups and preparation method and application thereof - Google Patents

Adsorption resin containing metal groups and preparation method and application thereof Download PDF

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CN116178606B
CN116178606B CN202310465504.XA CN202310465504A CN116178606B CN 116178606 B CN116178606 B CN 116178606B CN 202310465504 A CN202310465504 A CN 202310465504A CN 116178606 B CN116178606 B CN 116178606B
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resin
adsorption
metal
carbonyl compounds
polystyrene skeleton
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CN116178606A (en
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阎虎生
崔强
刘杰
孙强
陈利
李晓蒙
马玉新
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Nankai Cangzhou Bohai New Area Green Chemical Research Co ltd
Tianjin Nankai Hecheng Science & Technology Co ltd
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Nankai Cangzhou Bohai New Area Green Chemical Research Co ltd
Tianjin Nankai Hecheng Science & Technology Co ltd
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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
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • 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
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • 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
    • B01J20/28014—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 form
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • 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
    • 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
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention belongs to the technical field of high polymer resin materials, and particularly relates to an adsorption resin containing metal groups, and a preparation method and application thereof. The preparation method of the adsorption resin containing the metal groups comprises the following steps: (1) Carrying out copolymerization reaction on styrene, a cross-linking agent, a pore-forming agent and an initiator, and then carrying out halogenation reaction to obtain halogenated polystyrene skeleton resin; or, carrying out copolymerization reaction on a styrene monomer, a cross-linking agent, a pore-forming agent and an initiator to obtain halogenated polystyrene skeleton resin; (2) And (3) reacting the halogenated polystyrene skeleton resin with metal magnesium or organic lithium to obtain the modified polystyrene skeleton resin. According to the invention, the organic metal groups are introduced into the resin to form the functional groups with very high reactivity, so that the adsorption resin with strong adsorption effect and high adsorption selectivity on carbonyl compounds is formed, and the adsorption resin can adsorb carbonyl compounds from solution, gas phase and cigarette smoke, and has wide application range and high adsorption removal rate.

Description

Adsorption resin containing metal groups and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer resin materials, and particularly relates to an adsorption resin containing metal groups, and a preparation method and application thereof.
Background
Carbonyl compounds (including aldehydes and ketones) are important chemical raw materials, and are discharged during the production of chemical products using the carbonyl compounds. Many carbonyl compounds such as formaldehyde and acetaldehyde are volatile harmful gases, have strong toxicity and irritation, and the content of the carbonyl compounds in air or water exceeds a certain concentration to cause obvious discomfort of a human body, and chronic rhinitis and even functional injuries of a nervous system, an immune system and the like can be caused by long-term contact.
Current methods for removing carbonyl compounds include plasma treatment, photocatalyst catalysis, metal oxide oxidation, adsorbent adsorption, and the like. Adsorbent adsorption is considered to be a low cost, simple to operate, and capable of selectively reducing carbonyl compound content compared to other methods.
The adsorption resin is a cross-linked polymer material formed by organic high polymer polymerization and is used for adsorbing a certain compound or a certain class of compounds from a solution or adsorbing a certain gaseous compound or a certain class of gaseous compounds from a gas phase. At present, the adsorption mechanism of the reported adsorption resin mainly comprises: the adsorbate is adsorbed onto the resin using van der Waals, hydrophobic, ionic, coordination, hydrogen bonding, covalent or other chemical bonding. In contrast, adsorption by chemical bonds has the advantage of high adsorption selectivity. However, the selectivity and removal rate of carbonyl compounds of the existing adsorption materials using chemical bonds as the driving force for adsorption are still low.
Therefore, developing an adsorption resin capable of efficiently and selectively adsorbing carbonyl compounds from liquid or gaseous systems is of great significance for removing carbonyl compounds from different systems and reducing the potential hazard of carbonyl compounds.
Disclosure of Invention
The invention aims to provide a preparation method of a metal group-containing adsorption resin, and the metal group-containing adsorption resin prepared by the method has good adsorption capacity on carbonyl chemicals in a solution system, a gas phase system and cigarette smoke.
The invention also aims to provide the adsorption resin containing the metal groups, which has good adsorption capacity to carbonyl chemicals in a solution system, a gas phase system and cigarette smoke, and can effectively reduce the content of the carbonyl compounds.
Furthermore, the invention aims to provide the application of the adsorption resin containing the metal groups.
In order to achieve the above object, the preparation method of the adsorption resin containing metal groups of the invention adopts the following technical scheme:
a method for preparing an adsorption resin containing metal groups, comprising the steps of:
(1) Carrying out copolymerization reaction on styrene, a cross-linking agent, a pore-forming agent and an initiator, and then reacting a copolymerization product with halogen to obtain halogenated polystyrene skeleton resin;
or, carrying out copolymerization reaction on a styrene monomer, a cross-linking agent, a pore-forming agent and an initiator to obtain halogenated polystyrene skeleton resin;
the styrene monomer is at least 2 of styrene, chloromethyl styrene, bromomethyl styrene, chlorostyrene and bromostyrene;
(2) And (3) reacting the halogenated polystyrene skeleton resin with metal magnesium or organic lithium to obtain the modified polystyrene skeleton resin.
The preparation method of the adsorption resin containing the metal groups comprises the steps of preparing the resin containing the halogenated polystyrene skeleton through copolymerization, and then reacting the resin containing the halogenated polystyrene skeleton with magnesium metal or organic lithium to prepare the adsorption resin containing the metal groups. The invention prepares the halogenated polystyrene skeleton resin to improve the activity of subsequent reaction, and then introduces organic metal groups into the resin through the reaction with metal magnesium or organic lithium, so that the functional groups with very high reaction activity can be formed, thereby preparing the adsorption resin with strong adsorption effect and high adsorption selectivity on carbonyl compounds.
The adsorption resin prepared by the invention can efficiently and selectively adsorb carbonyl compounds from solution or adsorb gaseous carbonyl compounds from gas phase, and the adsorption mechanism is that the carbonyl compounds and organic metal groups on the resin form stable compounds to be fixed on the resin, thus playing an adsorption role. The adsorption principle and the reaction process are as follows:
the crosslinking agent should contain 2 or more double bonds, which function to crosslink the polymer formed by the functional monomer to form a stable three-dimensional network. Preferably, the cross-linking agent is selected from one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl itaconate, triallyl cyanurate, triallyl isocyanurate. The cross-linking agent is singly used or 2 or more than 2 cross-linking agents are used in a compound way, so that a better cross-linking effect can be achieved.
The porogen does not participate in the reaction throughout the reaction, and the porous resin is formed by the action of the porogen. Further, the pore-forming agent is selected from one or more of toluene, ethylbenzene, xylene, hexane, heptane, octane, isooctane, dodecane, kerosene, liquid wax, ethyl acetate, butyl acetate, hexyl acetate, propyl ether, butyl ether, pentyl ether, hexyl ether, petroleum ether, butanol, hexanol, cyclohexanol, isooctanol, octanol, heptanol, nonanol.
The initiator to be used in the present invention is not particularly limited, and it is only required to satisfy the polymerization reaction demand. Preferably, the initiator is azobisisobutyronitrile or dibenzoyl peroxide.
Preferably, the organic lithium is one or a combination of several of ethyl lithium, n-butyl lithium, tertiary butyl lithium and amyl lithium.
Further, the copolymerization is a suspension polymerization in which the reactants are mixed and dispersed in an aqueous phase. By adopting suspension polymerization reaction, the porous adsorption resin with better adsorption performance on carbonyl compounds can be obtained.
In order to achieve both the reaction efficiency and the resin adsorption performance, preferably, the temperature of the copolymerization reaction is 70-80 ℃ and the time is 10-12 hours; the reaction temperature of the halogenated polystyrene skeleton resin and the metal magnesium is 60-70 ℃ and the reaction time is 7-9 h; the reaction temperature of the halogenated polystyrene skeleton resin and the organic lithium is 20-30 ℃ and the reaction time is 7-9 h.
The adsorption resin containing the metal groups is prepared by adopting the preparation method.
The adsorption resin containing the metal groups plays a role in adsorbing the carbonyl compound by forming a stable covalent bond compound with the carbonyl compound, and has the advantages of strong adsorption effect and high adsorption selectivity. The carbonyl compounds which can be adsorbed by the resin containing the organic metal groups comprise aldehyde compounds (such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, glutaraldehyde, acrolein, crotonaldehyde and the like) and ketone compounds (such as acetone, butanone, pentanone, cyclohexanone, methyl isobutyl ketone, diketene and the like), and the application range is wide.
The invention also provides application of the adsorption resin containing the metal groups, in particular application of the adsorption resin containing the metal groups as an adsorption material in adsorbing carbonyl compounds.
Further, the application is: the use of an adsorption resin containing metal groups as an adsorption material for adsorbing carbonyl compounds in a solution; or as an adsorbent material for adsorbing carbonyl compounds in air; or as a filter material in adsorbing carbonyl compounds in cigarette smoke.
The metal group-containing adsorption resin provided by the invention has specific application range including but not limited to: the carbonyl compound in the adsorption solution achieves the separation and purification of the carbonyl compound; removing carbonyl compounds in wastewater containing the carbonyl compounds by adsorption; removing carbonyl compounds serving as impurities from the solution by adsorption; the adsorption of carbonyl compounds in the cigarette smoke reduces the toxicity; adsorption of carbonyl compounds in the air contaminated with carbonyl compounds to purify the air, etc.
Adsorption experiments in different media confirmed that: according to the preparation method of the adsorption resin containing the metal groups, the prepared adsorption resin containing the metal groups can effectively reduce the content of carbonyl chemicals in a solution system, a gas phase system and cigarette smoke. In the solution system, the adsorption rate of the adsorption resin containing the metal groups on carbonyl compounds (formaldehyde, acetaldehyde, butyraldehyde, acrolein, acetone, butanone, cyclohexanone and methyl isobutyl ketone) reaches 73.2% -99.3%; in a gas phase system, the adsorption capacity of the adsorption resin containing the metal groups on carbonyl compounds (formaldehyde, acetaldehyde, butyraldehyde, acrolein, acetone and butanone) reaches 19.8-48.3 mg/g; in cigarette smoke, the content reduction rate of the adsorption resin containing the metal groups to carbonyl compounds (formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, acetone and butanone) reaches 13.5% -75.2%. The adsorption resin containing metal groups has wide application range, and is suitable for removing carbonyl compounds in different media.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention.
The preparation method of the adsorption resin containing the metal groups comprises the following steps:
(1) Carrying out copolymerization reaction on styrene, a cross-linking agent, a pore-forming agent and an initiator, and then reacting a copolymerization product with halogen to obtain halogenated polystyrene skeleton resin;
or, carrying out copolymerization reaction on a styrene monomer, a cross-linking agent, a pore-forming agent and an initiator to obtain halogenated polystyrene skeleton resin; the styrene monomer is at least 2 of styrene, chloromethyl styrene, bromomethyl styrene, chlorostyrene and bromostyrene;
(2) And (3) reacting the halogenated polystyrene skeleton resin with metal magnesium or organic lithium to obtain the modified polystyrene skeleton resin.
In the step (1), the cross-linking agent is selected from one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl itaconate, triallyl cyanurate and triallyl isocyanurate. The cross-linking agent is singly used or 2 or more than 2 cross-linking agents are used in a compound way, so that a better cross-linking effect can be achieved. Further, the amount of the crosslinking agent is 0.3 to 3 times of the mass of the reaction monomer.
The pore-forming agent is selected from one or more of toluene, ethylbenzene, xylene, hexane, heptane, octane, isooctane, dodecane, kerosene, liquid wax, ethyl acetate, butyl acetate, hexyl acetate, propyl ether, butyl ether, amyl ether, hexyl ether, petroleum ether, butanol, hexanol, cyclohexanol, isooctanol, octanol, heptanol and nonanol. The consumption of the pore-forming agent is 1.0-3.5 times of the mass of the reaction monomer.
Preferably, the initiator is azobisisobutyronitrile or dibenzoyl peroxide. The amount of the initiator is 1% -8% of the mass of the reaction monomer.
The organic lithium is one or a combination of more of ethyl lithium, n-butyl lithium, tertiary butyl lithium and amyl lithium.
Further, the copolymerization is a suspension polymerization in which the reactants are mixed and dispersed in an aqueous phase. The reactant comprises styrene or styrene monomer, cross-linking agent, pore-forming agent and initiator. By adopting suspension polymerization reaction, the porous adsorption resin with better adsorption performance on carbonyl compounds can be obtained.
Further, the aqueous phase is composed of polyvinyl alcohol, salt and water. The salt is sodium chloride or sodium sulfate. Every 350-500 mL of water, the dosage of the corresponding polyvinyl alcohol is 0.5-1.2 g, and the dosage of the corresponding salt is 3-40 g.
The temperature of the copolymerization reaction is 70-80 ℃ and the time is 10-12 h.
The reaction temperature of the halogenated polystyrene skeleton resin and the metal magnesium is 60-70 ℃ and the reaction time is 7-9 h; the usage amount of magnesium corresponding to each 20g of halogenated polystyrene skeleton resin is 3.5-6.5 g.
The reaction temperature of the halogenated polystyrene skeleton resin and the organic lithium is 20-30 ℃ and the reaction time is 7-9 h; the amount of organic lithium corresponding to each 20g of halogenated polystyrene skeleton resin is 8-20 g.
Example 1
The preparation method of the adsorption resin containing the metal groups provided by the embodiment comprises the following steps:
(1) 0.72g of polyvinyl alcohol (model 1788) was dissolved in 350mL of distilled water, and 3.6g of sodium chloride was dissolved therein to obtain an aqueous phase.
25.4g of styrene, 5.2g of bromostyrene, 9.4g of divinylbenzene, 16g of toluene, 20g of liquid wax and 0.4g of dibenzoyl peroxide were mixed and stirred to dissolve the solids completely to obtain an oil phase.
(2) And (3) adding the oil phase obtained in the step (1) into the water phase, starting mechanical stirring, adjusting the stirring speed to disperse the oil phase into small oil droplets, heating to 80 ℃ and maintaining the system temperature for 12 hours. Stopping heating, cooling the system, filtering, collecting, washing with hot water for multiple times, and air drying to obtain resin containing halogenated polystyrene skeleton.
(3) 20g of the resin containing the halogenated polystyrene skeleton obtained in the step (2) was suspended in 160mL of tetrahydrofuran, 3.5g of magnesium turnings were added under stirring, the mixture was heated to 66℃for reflux reaction for 8 hours, and then the resin was washed with tetrahydrofuran and petroleum ether, respectively, and dried in vacuo to obtain the metal group-containing adsorbent resin of example 1.
Example 2
In the method for producing a metal group-containing adsorbent resin of this example, steps (1) and (2) are the same as in example 1, and step (3) is: suspending 20g of the resin containing the halogenated polystyrene skeleton obtained in the step (2) in 160mL of tetrahydrofuran, stirring and cooling to-78 ℃, dropwise adding 60mL of toluene solution of n-butyllithium (containing 9.3g of n-butyllithium), heating to 25 ℃ for reaction for 8 hours, filtering out the resin, washing the resin with tetrahydrofuran and methanol for multiple times, and vacuum drying to obtain the adsorption resin containing the metal groups in the example 2.
Example 3
The preparation method of the adsorption resin containing the metal groups in the embodiment comprises the following steps:
(1) 1.05g of polyvinyl alcohol (model 1788) was dissolved in 350mL of distilled water, and 39g of sodium chloride was dissolved therein to obtain an aqueous phase.
10.9g of styrene, 29.1g of divinylbenzene, 16g of xylene, 20g of isooctanol and 0.8g of dibenzoyl peroxide were mixed and stirred to dissolve the solids completely to obtain an oil phase.
(2) And (3) adding the oil phase obtained in the step (1) into the water phase, starting mechanical stirring, adjusting the stirring speed to disperse the oil phase into small oil droplets, heating to 80 ℃ and maintaining the system temperature for 12 hours. Stopping heating, cooling the system, filtering, collecting, washing with hot water for several times, and oven drying.
After drying, 300mL of dichloroethane, 50g of magnesium powder and 70mL of bromine are added into the reaction product, the mixture is heated to 35 ℃ with stirring to react for 8 hours, then 60mL of 4mol/L sodium hydroxide solution is added, stirring is carried out for 3 hours, 100mL of concentrated hydrochloric acid is added into the filtered solid, stirring is carried out for 12 hours, the filtered resin is washed with water and ethanol for multiple times, and the resin containing halogenated polystyrene skeleton is obtained after drying.
(3) 20g of the resin containing the halogenated polystyrene skeleton obtained in the step (2) was suspended in 160mL of tetrahydrofuran, 6.2g of magnesium turnings were added under stirring, the mixture was heated to 66℃for reflux reaction for 8 hours, and then the resin was washed with tetrahydrofuran and petroleum ether, respectively, and dried under vacuum to obtain the resin containing the organometallic group of example 3.
Example 4
In the method for producing a metal group-containing adsorbent resin of this example, steps (1) and (2) are the same as in example 3, and step (3) is: suspending 20g of the resin containing the halogenated polystyrene skeleton obtained in the step (2) in 160mL of tetrahydrofuran, stirring and cooling to-78 ℃, dropwise adding 45mL of toluene solution of n-butyllithium (containing 16.5g of n-butyllithium), heating to 25 ℃ for reaction for 8 hours, filtering out the resin, washing the resin with tetrahydrofuran and methanol for multiple times, and vacuum drying to obtain the adsorption resin containing the metal groups in the example 4.
Example 5
The preparation method of the adsorption resin containing the metal groups in the embodiment comprises the following steps:
(1) 0.5g of polyvinyl alcohol (model 1788) polyvinyl alcohol was dissolved in 500mL of distilled water, and 10g of sodium sulfate was dissolved therein to obtain a water phase;
62.4g of styrene, 33.2g of chloromethyl styrene, 31.9g of divinylbenzene, 68g of xylene, 136g of octanol and 2.6g of azobisisobutyronitrile were mixed and stirred to dissolve the solids completely, giving an oil phase.
(2) Adding the oil phase obtained in the step (1) into the water phase, starting mechanical stirring, adjusting the stirring speed to disperse the oil phase into small oil droplets, heating to 75 ℃ and maintaining the system temperature for 12 hours. Stopping heating, cooling the system, filtering, collecting, washing with hot water for multiple times, and air drying to obtain resin containing halogenated polystyrene skeleton.
(3) 20g of the resin containing the halogenated polystyrene skeleton obtained in the step (2) was suspended in 160mL of tetrahydrofuran, 5.7g of magnesium turnings were added under stirring, the mixture was heated to 66℃for reflux reaction for 8 hours, and then the resin was washed with tetrahydrofuran and petroleum ether, respectively, and dried in vacuo to obtain the metal group-containing adsorbent resin of example 5.
Example 6
In the method for producing a metal group-containing adsorbent resin of this example, steps (1) and (2) are the same as in example 5, and step (3) is: and (3) stirring and cooling 20g of the resin containing the halogenated polystyrene skeleton obtained in the step (2) to-78 ℃, dropwise adding 39mL of toluene solution of n-butyllithium (containing 15.2g of n-butyllithium), heating to 25 ℃ for reaction for 8 hours, filtering out the resin, washing the resin with tetrahydrofuran and methanol for multiple times, and vacuum drying to obtain the adsorption resin containing the metal groups in the example 6.
Test example 1
1g of the adsorption resin containing the metal groups obtained in examples 1 to 6 was respectively suspended in 25mL of an aqueous solution of formaldehyde with a concentration of 1000ppm, and shaken at room temperature for 30min, and then the formaldehyde content in the supernatant was measured and the removal rate was calculated with reference to GB/T9733-2008. The test procedures for other carbonyl compounds acetaldehyde, butyraldehyde, acrolein, acetone, butanone, cyclohexanone, methyl isobutyl ketone were performed with reference to formaldehyde, and the results are shown in Table 1.
TABLE 1 removal Rate of carbonyl Compounds from solution by adsorption resin containing Metal groups (%)
As is clear from Table 1, the adsorption rate of the metal group-containing adsorption resin of the present invention to carbonyl compounds (formaldehyde, acetaldehyde, butyraldehyde, acrolein, acetone, butanone, cyclohexanone, methyl isobutyl ketone) in the solution system was 73.2% -99.3% within 30 min. Therefore, the organic metal groups can be introduced into the resin through the reaction of the halogenated polystyrene skeleton resin and the metal magnesium or the organic lithium to form the functional groups with very high reactivity, so that the adsorption resin with strong adsorption effect on carbonyl compounds and high adsorption efficiency is prepared.
Test example 2
10g of the metal group-containing adsorption resins obtained in examples 1 to 6 were packed in respective columns, air having a concentration of 30mg/m3 of each carbonyl compound was passed through the resin column at a flow rate of 30mL/min, and the carbonyl compound at the outlet was collected, and the concentration of each carbonyl compound was measured with reference to GB/T9733-2008. When the concentration of the carbonyl compound at the outlet reaches 0.5mg/m3 of air, the leakage volume is defined, and the adsorption quantity of the adsorption resin containing the metal groups on each carbonyl compound is calculated by the leakage volume, wherein the unit is mg/g. The results are shown in Table 2.
TABLE 2 adsorption of carbonyl Compounds in air by adsorption resin containing Metal groups (mg/g)
As is clear from Table 2, the adsorption amount of the metal group-containing adsorbent resin of the present invention to various carbonyl compounds in a gas phase system is 19.8 to 48.3mg/g. Wherein, the resin material obtained by modifying the halogenated polystyrene skeleton resin by adopting organic lithium has better adsorption performance improvement degree than the adsorption material obtained by modifying the halogenated polystyrene skeleton resin by adopting metal magnesium.
Test example 3
40mg of the adsorption resin containing metal groups obtained in examples 1 to 6 was added to a cigarette filter of the same specification, and the concentration of carbonyl compounds after passing through the filter was measured by referring to YC/T254-2008 "measurement of Main carbonyl Compound in Main stream cigarette Smoke" and calculated as the reduction rate of carbonyl compounds by taking the same filter without resin as a control. The results are shown in Table 3.
TABLE 3 reduction of carbonyl Compounds in cigarette smoke by adsorption resins containing Metal groups (%)
As shown in Table 3, the content reduction rate of the adsorption resin containing the metal groups to carbonyl compounds (formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, acetone and butanone) in cigarette smoke reaches 13.5% -75.2%, which is beneficial to improving the quality of cigarettes and is suitable for application in cigarette filter materials.
In conclusion, the adsorption resin containing metal groups has wide application range and good popularization and application prospect in the application of removing carbonyl compounds in different media.

Claims (7)

1. A method for preparing an adsorption resin containing metal groups, comprising the steps of:
(1) Carrying out copolymerization reaction on styrene, a cross-linking agent, a pore-forming agent and an initiator, and then reacting a copolymerization product with halogen to obtain halogenated polystyrene skeleton resin;
or, carrying out copolymerization reaction on a styrene monomer, a cross-linking agent, a pore-forming agent and an initiator to obtain halogenated polystyrene skeleton resin;
the styrene monomer is at least 2 of styrene, chloromethyl styrene, bromomethyl styrene, chlorostyrene and bromostyrene;
(2) Reacting halogenated polystyrene skeleton resin with magnesium metal to obtain adsorption resin containing metal groups;
wherein the copolymerization reaction is suspension polymerization reaction carried out by mixing reactants and dispersing the reactants in an aqueous phase; the temperature of the copolymerization reaction is 70-80 ℃ and the time is 10-12 h; the reaction temperature of the halogenated polystyrene skeleton resin and the metal magnesium is 60-70 ℃ and the reaction time is 7-9 h; the usage amount of the corresponding metal magnesium of each 20g of the halogenated polystyrene skeleton resin is 3.5-6.5 g.
2. The method for producing a metal group-containing adsorbent resin according to claim 1, wherein the crosslinking agent is one or more selected from divinylbenzene, ethylene glycol dimethacrylate, allyl itaconate, triallyl cyanurate, triallyl isocyanurate.
3. The method of preparing a metal group containing adsorption resin according to claim 1, wherein the porogen is selected from one or more of toluene, ethylbenzene, xylene, hexane, heptane, octane, isooctane, dodecane, kerosene, liquid wax, ethyl acetate, butyl acetate, hexyl acetate, propyl ether, butyl ether, pentyl ether, hexyl ether, petroleum ether, butanol, hexanol, cyclohexanol, isooctanol, octanol, heptanol, nonanol.
4. The method for producing a metal group-containing adsorbent resin according to claim 1, wherein the initiator is azobisisobutyronitrile or dibenzoyl peroxide.
5. A metal group-containing adsorbent resin produced by the process for producing a metal group-containing adsorbent resin according to any one of claims 1 to 4.
6. Use of a metal group containing adsorption resin according to claim 5 for adsorbing carbonyl compounds.
7. Use of the metal group-containing adsorption resin according to claim 6 as an adsorption material for adsorbing carbonyl compounds in solution; or as an adsorbent material for adsorbing carbonyl compounds in air; or as a filter material in adsorbing carbonyl compounds in cigarette smoke.
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