CN103044640B - Attapulgite grafted polystyrene hybrid particle and preparation method thereof - Google Patents
Attapulgite grafted polystyrene hybrid particle and preparation method thereof Download PDFInfo
- Publication number
- CN103044640B CN103044640B CN201210555915.XA CN201210555915A CN103044640B CN 103044640 B CN103044640 B CN 103044640B CN 201210555915 A CN201210555915 A CN 201210555915A CN 103044640 B CN103044640 B CN 103044640B
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- hybrid particle
- preparation
- polystyrene
- sieved
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to an attapulgite grafted polystyrene hybrid particle and a preparation method thereof. The organic-inorganic hybrid particle with high grafting ratio is prepared from main raw materials comprising attapulgite clay and styrene. Nano-scale attapulgite with aryl tertiary amine group on the surface and benzoyl peroxide form an oxidation-reduction initiating system through molecular design, and radical is generated on the surface of the attapulgite, so surface initiating polymerization of styrene is realized. Point position capable of initiating polymerization is introduced into the surface of each particle, so that a monomer starts to be polymerized on the surface of the particle and grafting polymerization is realized. By the method, the introduction difficulty of the initiating group is overcome and the surface initiating polymerization of the oil-soluble monomer in solution is realized. The process is simple and safe in operation. The prepared hybrid particle has high hydrophobicity, and the surface polystyrene grafting ratio of the prepared hybrid particles is 25.68 percent.
Description
Technical field
The present invention relates to a kind of attapulgite grafted polystyrene hybrid particle and preparation method thereof.
Background technology
Attapulgite clay take Attapulgite as the manosil AS salt mine containing Shuifu County's magnesium that main component a kind of has specialty fibers shape crystal habit structure.It is a kind of clay mineral of uniqueness, and the desirable molecular formula of attapulgite is (Mg, Al, Fe)
5si
8o
20(HO)
2(OH
2)
4.4H
2o.In order to improve the effective deployment conditions of attapulgite in polymeric matrix, usually suitable modification is carried out to it.Conventional method of modifying is mainly divided into physically modified and chemical modification.Organic modifiers is adsorbed on nanoparticle surface mainly through Van der Waals force, hydrogen bond force equimolecular intermolecular forces by physically modified, coating layer is formed on surface, thus reduction surface tension, reduce the reunion between nanoparticle, reach the object of uniform and stable dispersion, be also called the modification of absorption parcel in this way.Chemical modification is surface-modifying agent etc. and the existing group generation chemical reaction of surface of inorganic particles, and properties-correcting agent etc. receive particle surface with chemical bond-linking, to reach the object of modification.The main path of surface chemical modification has tensio-active agent activation method, surface grafting polymerization method and plasma body and radiation-initiated polymerization method.Surface grafting polymerization method mainly utilizes attapulgite's surface can reactive group, its silane coupling agent is adopted to introduce polymerizable double bond or can initiating activity point to its modification, as: Lin Wei etc. prepare attapulgite-water-borne polyurethane nano composite leather coating agent (publication number: CN101565588, a kind of organic attapulgite-water-borne polyurethane nano composite leather coating agent and preparation method thereof) by situ aggregation method after adopting attapulgite modified by silane coupling agent; The vinylformic acid that Wang Aiqin etc. adopt part to neutralize and attapulgite carry out graft copolymerization crosslinking and have prepared a kind of organic-inorganic composite water retaining agent (publication number: CN1438256, organic-inorganic composite water retaining agent and preparation method thereof) under initiator exists.
Polystyrene (PS) is a kind of exploitation important thermoplastics comparatively early, has the good transparency, chemical stability and weathering resistance.PS molecular chain is grafted to the brilliant surface of the single rod of attapulgite, a kind of particle of hybrid material can be obtained, and effectively improve the brilliant agglomeration in the polymer of attapulgite rod, realize nano-scale dispersion.
Adopt attapulgite to prepare as inorganic phase the advantage that compound ability two can give full play to both performances, have simultaneously and reduce costs, effectively utilize the economic benefit of attapulgite natural nano-material.Sun Hongxiu, the people such as Zhuan Wei have adopted in-situ suspension polymerization legal system for acrylate copolymer/attapulgite composite material, adopt soap-free emulsion legal system for poly-methylpropanoic acid methyl esters/attapulgite modified complex microsphere, and have studied performance (the preparation and property research of acrylate copolymer/organic-silicon-modified attapulgite composite material of matrix material, plastics industry, the 9th phase in 2011; Soap-free emulsion legal system for polymethylmethacrylate/attapulgite modified microballoon and performance study thereof, Speciality Petrochemicals, the 5th phase in 2011).
Aforesaid method mainly adopts in-situ polymerization preparation/polymkeric substance attapulgite composite material according to " graft though " principle, situ aggregation method adopts one-shaping technique to avoid the thermal destruction of polymkeric substance in extrusion, and the dispersion of inorganic phase is better than mechanical blending method, but due to the microinhomogeneity of copolymerization system and the steric effect of macromolecular chain, polymkeric substance is little with chemical bond grafting attapulgite reaction probability of occurrence, therefore percentage of grafting is not high, effective hybridization network structure cannot be formed, the poor dispersion of attapulgite in polymerization, easy gathering, utilization ratio is not high, can not better in conjunction with the advantage of attapulgite and polymer performance, the performance of matrix material is not high.
Summary of the invention
In order to overcome the weak point of " graft though " principle, the invention provides in a kind of hybrid particle: polystyrene graft is to the preparation method of attapulgite, the method utilizes at attapulgite's surface chemical bonding primary amino, again with 4-(diethylin) salicylic aldehyde forms stable schiff bases, aryl tertiary amine group is introduced in attapulgite's surface, utilize peroxidation phenyl-diformyl-aryl tertiary amine redox initiation system, cause styrene monomer in attapulgite's surface graft polymerization, by chemical bonding by polystyrene graft on attapulgite, attapulgite and polymer compatibility can be significantly improved, give full play to both performances.
Attapulgite grafted polystyrene hybrid particle of the present invention is grafted with polystyrene on attapulgite.
The percentage of grafting of the polystyrene of described hybrid particle is 25.68%.
Another object of the present invention is to the preparation method that a kind of polystyrene graft attapulgite is provided.This preparation method adopts solution system, and graft polymerization rates is fast, reacting balance safety; Simple to operate, easy.
Attapulgite grafted polystyrene hybrid particle of the present invention, prepare according to the following steps:
(1) attapulgite acid activation: nano level attapulgite is scattered in the acid that hydrogen ion concentration is 1mol/L with mass ratio 1:10-1:20, filter after 24 hours, be washed with distilled water to neutrality, vacuum-drying, grinding is sieved, and obtains acid activation attapulgite;
(2) be that 1:20-1:50 is scattered in organic solvent by acid activation attapulgite in step (1) with mass ratio, ultrasonic disperse 30-60min, drips primary aminoalkoxysilanes, 80-140 DEG C of reaction 6-10h; Reaction terminates rear mistake and filters solvent, and with absolute ethanol washing several, vacuum-drying, grinding is sieved, and obtains the attapulgite of surface chemistry bonding primary amino;
(3) by the attapulgite of surface chemistry bonding primary amino in step (2) dispersion dehydrated alcohol, ultrasonic disperse 30-60min, add 4-(diethylin) salicylic aldehyde and appropriate anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out upper strata suspension, cross filter after solvent with washed with isopropyl alcohol for several times, vacuum-drying, pulverizing, grinding are sieved, and obtain the surperficial attapulgite with redox initiator activity with aryl tertiary amine group;
(4) attapulgite with aryl tertiary amine group surperficial in step (3) is dispersed in 150ml toluene, ultrasonic disperse 30-60min, add vinylbenzene, the oxygen in logical nitrogen 30min removing system, stirs and is warming up to 40-60 DEG C, add peroxidation phenyl-diformyl initiator, reaction 8-12h, takes out for the polymkeric substance removing surface adsorption by toluene wash after being filtered by product, vacuum-drying, grinding is sieved, and obtains attapulgite grafted polystyrene hybrid particle.
Wherein in step (1), acid used is hydrochloric acid or dilute sulphuric acid.
Wherein in step (2), organic solvent used is toluene or dimethylbenzene.
The primary aminoalkoxysilanes that wherein step (2) is wherein used is the one in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-aminopropyltriethoxy dimethoxysilane, and the mass ratio of its consumption and attapulgite is 1:1-1:2.
The wherein attapulgite of the surface bond primary amino described in step (3) and 4-(diethylin) mass ratio of salicylic aldehyde is 1:1-1:1.5.
Wherein the mass ratio of the styrene monomer described in step (4) and solvent toluene should control at 8%-15%.
Oil soluble organic peroxy initiator wherein used in step (4) is the one in peroxidation phenyl-diformyl, dicumyl peroxide, the benzoyl peroxide tert-butyl ester.Consumption is the 1%-4% of monomer mass.
The advantage of attapulgite grafted polystyrene hybrid particle preparation method of the present invention is:
(1) adopt oxidation-reduction trigger system, temperature of reaction is low, and heat radiation is easily, simple to operate.
(2) adopt solution system, product postprocessing is simple and easy.
(3) according to " surperficial Inducing Graft Polymerization " principle, the aryl tertiary amine group that can produce free radical is introduced in attapulgite's surface, oxidation-reduction trigger system is formed with the organic peroxy class initiator in oil phase, graft polymerization reaction is occurred in attapulgite's surface, overcomes the defect that situ aggregation method percentage of grafting is low; Meanwhile, it also avoid in " surperficial Inducing Graft Polymerization " reaction in the active drawback reduced of initiator group that particle surface is introduced.
The calculating of percentage of grafting: learn that PS starts to decompose near 320 DEG C by consulting pertinent literature, therefore adopt thermal weight loss (TG) method to measure the percentage of grafting of hybrid particle surface PS.Be calculated as follows percentage of grafting (γ
g)
γ in formula
gfor percentage of grafting; m
1: the quality of graft product; m
2: the quality of the polymkeric substance of grafting.
Embodiment
The term used in the present invention, unless otherwise specified, generally has the implication that this ambit those of ordinary skill is understood usually.
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these embodiments just in order to demonstrate the invention, but not limit the scope of the invention by any way
Embodiment 1
Nano level attapulgite is dispersed in ultrasonic vibration 6 in the hydrochloric acid of 1mol/L, removes solvent after leaving standstill 24h, washing is to neutral, and vacuum-drying, grinding is sieved, and obtains acid activation attapulgite.
Getting 4g acid activation attapulgite soil is scattered in 100mL toluene, ultrasonic disperse 60min, under agitation condition, drips 8g γ-aminopropyl triethoxysilane, after dripping, be heated to 80 DEG C, reaction 12h, after reaction terminates, except desolventizing, vacuum-drying, grinding is sieved, and obtains the attapulgite of surface chemistry bonding primary amino.
The attapulgite 1g getting surface chemistry bonding primary amino is dispersed in dehydrated alcohol, ultrasonic vibration 40min, add 1.5g4-(diethylin) salicylic aldehyde, appropriate anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out suspension, crosses and filters solvent, with washed with isopropyl alcohol several, vacuum-drying, grinding is sieved, and obtains the surperficial Functional attapulgite particle with aryl tertiary amine group.
Getting the surperficial attapulgite with aryl tertiary amine group of 0.5g is dispersed in 150ml toluene, ultrasonic disperse 50min, add 12g vinylbenzene, the oxygen in logical nitrogen 30min removing system, stirs and is warming up to 40 DEG C, add peroxidation phenyl-diformyl initiator, reaction 10h, takes out for the polymkeric substance removing surface adsorption by toluene wash after being filtered by product, vacuum-drying, grinding is sieved, and obtains attapulgite grafted polystyrene hybrid particle.
Embodiment 2
Nano level attapulgite is dispersed in ultrasonic vibration 30min in the dilute sulphuric acid of 0.5mol/L, removes solvent after leaving standstill 24h, washing is to neutral, and vacuum-drying, grinding is sieved, and obtains acid activation attapulgite.
Getting 4g acid activation attapulgite soil is scattered in 150mL toluene, ultrasonic disperse 30min, under agitation condition, drips 4g γ-aminopropyl triethoxysilane, after dripping, be heated to 110 DEG C, reaction 10h, after reaction terminates, except desolventizing, vacuum-drying, grinding is sieved, and obtains the attapulgite of surface chemistry bonding primary amino.
The attapulgite getting 1g surface chemistry bonding primary amino is dispersed in dehydrated alcohol, ultrasonic vibration 40min, add 1g4-(diethylin) salicylic aldehyde, appropriate anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out suspension, crosses and filters solvent, with washed with isopropyl alcohol several, vacuum-drying, grinding is sieved, and obtains the surperficial Functional attapulgite particle with aryl tertiary amine group.
Getting the surperficial attapulgite with aryl tertiary amine group of 0.5g is dispersed in 150ml toluene, ultrasonic disperse 35min, add 15g vinylbenzene, the oxygen in logical nitrogen 30min removing system, stirs and is warming up to 45 DEG C, add 0.6g peroxidation phenyl-diformyl initiator, reaction 8-12h, takes out for the polymkeric substance removing surface adsorption by toluene wash after being filtered by product, vacuum-drying, grinding is sieved, and obtains attapulgite grafted polystyrene hybrid particle.
Embodiment 3
Nano level attapulgite is dispersed in ultrasonic vibration 40min in the hydrochloric acid of 1mol/L, removes solvent after leaving standstill 24h, washing is to neutral, and vacuum-drying, grinding is sieved, and obtains acid activation attapulgite.
Getting 4g acid activation attapulgite soil is scattered in 100mL dimethylbenzene, ultrasonic disperse 40min, under agitation condition, drips 8g γ-aminopropyl triethoxysilane, after dripping, be heated to 140 DEG C, reaction 6h, after reaction terminates, except desolventizing, vacuum-drying, grinding is sieved, and obtains the attapulgite of surface chemistry bonding primary amino.
The attapulgite 1g getting surface chemistry bonding primary amino is dispersed in dehydrated alcohol, ultrasonic vibration 40min, add 1.5g4-(diethylin) salicylic aldehyde, appropriate anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out suspension, crosses and filters solvent, with washed with isopropyl alcohol several, vacuum-drying, grinding is sieved, and obtains the surperficial Functional attapulgite particle with aryl tertiary amine group.
Getting the surperficial attapulgite with aryl tertiary amine group of 0.5g is dispersed in 150ml toluene, ultrasonic disperse 40min, add 12g vinylbenzene, the oxygen in logical nitrogen 30min removing system, stirs and is warming up to 55 DEG C, add 0.24g dicumyl peroxide initiator, reaction 10h, takes out for the polymkeric substance removing surface adsorption by toluene wash after being filtered by product, vacuum-drying, grinding is sieved, and obtains attapulgite grafted polystyrene hybrid particle.
Embodiment 4
Nano level attapulgite is dispersed in ultrasonic vibration 50min in the hydrochloric acid of 1mol/L, removes solvent after leaving standstill 24h, washing is to neutral, and vacuum-drying, grinding is sieved, and obtains acid activation attapulgite.
Getting 4g acid activation attapulgite soil is scattered in 150mL dimethylbenzene, ultrasonic disperse 50min, under agitation condition, drips 4g γ-aminopropyl triethoxysilane, after dripping, be heated to 140 DEG C, reaction 8h, after reaction terminates, except desolventizing, vacuum-drying, grinding is sieved, and obtains the attapulgite of surface chemistry bonding primary amino.
The attapulgite 1g getting surface chemistry bonding primary amino is dispersed in dehydrated alcohol, ultrasonic vibration 40min, add 1g4-(diethylin) salicylic aldehyde, appropriate anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out suspension, crosses and filters solvent, with washed with isopropyl alcohol several, vacuum-drying, grinding is sieved, and obtains the surperficial Functional attapulgite particle with aryl tertiary amine group.
Getting the surperficial attapulgite with aryl tertiary amine group of 0.5g is dispersed in 150ml toluene, ultrasonic disperse 60min, add 18g vinylbenzene, the oxygen in logical nitrogen 30min removing system, stirs and is warming up to 40-60 DEG C, add 0.18g dicumyl peroxide initiator, reaction 10h, takes out for the polymkeric substance removing surface adsorption by toluene wash after being filtered by product, vacuum-drying, grinding is sieved, and obtains attapulgite grafted polystyrene hybrid particle.
Test one
Oleophylic is tested: select pure attapulgite, attapulgite grafted polystyrene hybrid particle, adds q. s. toluene in 100ml beaker, gets above-mentioned two kinds of particles a small amount of, then ultrasonic vibration 30min, than two kinds of dispersion of particles situations.
Lipophilicity
After ultrasonic vibration, pure attapulgite is deposited in bottom in a large number, limpider, and the attapulgite of polystyrene graft is suspended in toluene, and system is more muddy.The surface tension adding attapulgite and polar solvent after surperficial grafted polystyrene is described reduces surface polarity, and hybrid particle has lipophilicity well.
By consulting pertinent literature, By consulting literatures is known learns that PS starts to decompose near 320 DEG C, decompose and terminate, therefore adopt thermal weight loss (TG) method to measure the percentage of grafting of hybrid particle surface PS before and after 500 DEG C.Recording maximum percentage of grafting is 25.68%.
Claims (7)
1. a preparation method for attapulgite grafted polystyrene hybrid particle, is characterized in that step is as follows:
(1) attapulgite acid activation: nano level attapulgite is scattered in the acid that hydrogen ion concentration is 1mol/L with mass ratio 1:10-1:20, filter after 24 hours, be washed with distilled water to neutrality, vacuum-drying, grinding is sieved, and obtains acid activation attapulgite;
(2) be that 1:20-1:50 is scattered in organic solvent by acid activation attapulgite in step (1) with mass ratio, ultrasonic disperse 30-60min, drips primary aminoalkoxysilanes, 80-140 DEG C of reaction 6-10h; Reaction terminates rear mistake and filters solvent, and with absolute ethanol washing several, vacuum-drying, grinding is sieved, and obtains the attapulgite of surface chemistry bonding primary amino;
(3) by the attapulgite of surface chemistry bonding primary amino in step (2) dispersion dehydrated alcohol, ultrasonic disperse 30-60min, add 4-(diethylin) salicylic aldehyde and appropriate anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out upper strata suspension, cross filter after solvent with washed with isopropyl alcohol for several times, vacuum-drying, pulverizing, grinding are sieved, and obtain the surperficial attapulgite with redox initiator activity with aryl tertiary amine group;
(4) attapulgite with aryl tertiary amine group surperficial in step (3) is dispersed in 150ml toluene, ultrasonic disperse 30-60min, add vinylbenzene, the oxygen in logical nitrogen 30min removing system, stirs and is warming up to 40-60 DEG C, add peroxidation phenyl-diformyl initiator, reaction 8-12h, takes out for the polymkeric substance removing surface adsorption by toluene wash after being filtered by product, vacuum-drying, grinding is sieved, and obtains the attapulgite hybrid particle of polystyrene graft.
2. the preparation method of a kind of attapulgite grafted polystyrene hybrid particle according to claim 1, is characterized in that: described organic solvent is toluene or dimethylbenzene; Described acid is dilute hydrochloric acid or dilute sulphuric acid; Described oil soluble organic peroxy initiator is the one in peroxidation phenyl-diformyl, dicumyl peroxide, the benzoyl peroxide tert-butyl ester.
3. the preparation method of a kind of attapulgite grafted polystyrene hybrid particle according to claim 1, is characterized in that: described primary aminoalkoxysilanes is the one in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-aminopropyltriethoxy dimethoxysilane; The mass ratio of its consumption and attapulgite is 1:1-1:2.
4. the preparation method of a kind of attapulgite grafted polystyrene hybrid particle according to claim 1, is characterized in that: the percentage of grafting of the polystyrene of described hybrid particle is 25.68%.
5. the preparation method of a kind of attapulgite grafted polystyrene hybrid particle according to claim 1, is characterized in that: described initiator amount is the 1%-4% of monomer mass.
6. the preparation method of a kind of attapulgite grafted polystyrene hybrid particle according to claim 1, is characterized in that: described styrene monomer and the mass ratio of solvent toluene should control at 8%-15%.
7. the attapulgite grafted polystyrene hybrid particle prepared by method described in claim 1, is characterized in that, attapulgite is grafted with polystyrene, and the percentage of grafting of the polystyrene of described hybrid particle is 25.68%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210555915.XA CN103044640B (en) | 2012-12-20 | 2012-12-20 | Attapulgite grafted polystyrene hybrid particle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210555915.XA CN103044640B (en) | 2012-12-20 | 2012-12-20 | Attapulgite grafted polystyrene hybrid particle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103044640A CN103044640A (en) | 2013-04-17 |
| CN103044640B true CN103044640B (en) | 2015-02-04 |
Family
ID=48057520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210555915.XA Expired - Fee Related CN103044640B (en) | 2012-12-20 | 2012-12-20 | Attapulgite grafted polystyrene hybrid particle and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103044640B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152237A (en) * | 2015-08-30 | 2015-12-16 | 常州市鼎日环保科技有限公司 | Method for manufacturing attapulgite-based porous super-hydrophobicity materials |
| WO2020027735A1 (en) * | 2018-07-30 | 2020-02-06 | Agency For Science, Technology And Research | Silane grafted onto clay |
| CN109232817B (en) * | 2018-09-28 | 2020-10-30 | 常州大学 | Preparation method of in-situ reaction compatibilization polypropylene/attapulgite composite material |
| CN110669268A (en) * | 2019-10-09 | 2020-01-10 | 芜湖风雪橡胶有限公司 | Reinforced styrene butadiene rubber and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247807B (en) * | 2011-05-17 | 2013-09-25 | 江苏麦阁吸附剂有限公司 | Preparation method and usage of modified attapulgite adsorption material |
| CN102558461B (en) * | 2011-08-15 | 2013-09-18 | 中北大学 | Method for realizing styrene high-efficiency graft polymerization on silica gel micro-particle surfaces by using tertiary arylamine-BPO oxidation-reduction initiation system |
-
2012
- 2012-12-20 CN CN201210555915.XA patent/CN103044640B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103044640A (en) | 2013-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012699A (en) | Attapulgite grafted polymethyl methacrylate hybrid particle and preparation method thereof | |
| CN103044640B (en) | Attapulgite grafted polystyrene hybrid particle and preparation method thereof | |
| Iftekhar et al. | Synthesis of novel GA-g-PAM/SiO2 nanocomposite for the recovery of rare earth elements (REE) ions from aqueous solution | |
| Xu et al. | New double network hydrogel adsorbent: Highly efficient removal of Cd (II) and Mn (II) ions in aqueous solution | |
| Liu et al. | Adsorption of Au (III), Pd (II), and Pt (IV) from aqueous solution onto graphene oxide | |
| Etmimi et al. | Synthesis and characterization of polystyrene‐graphite nanocomposites via surface RAFT‐mediated miniemulsion polymerization | |
| CN103025654B (en) | The preparation method and application of the Graphene that coordinating group is modified | |
| Lapwanit et al. | Chelating magnetic copolymer composite modified by click reaction for removal of heavy metal ions from aqueous solution | |
| Pandey et al. | Graft copolymerization of ethylacrylate onto xanthan gum, using potassium peroxydisulfate as an initiator | |
| Wang et al. | Stimuli-responsive polymer covalent functionalization of graphene oxide by Ce (IV)-induced redox polymerization | |
| Lin et al. | Fabrication of photo-responsive cellulose based intelligent imprinted material and selective adsorption on typical pesticide residue | |
| Hosseinzadeh et al. | Synthesis of magnetic functionalized MWCNT nanocomposite through surface RAFT co-polymerization of acrylic acid and N-isopropyl acrylamide for removal of cationic dyes from aqueous solutions | |
| CN109718745B (en) | Bernoulli type magnetic imprinting nanosheet and preparation method and application thereof | |
| Hosseinzadeh et al. | Preparation of novel multi-walled carbon nanotubes nanocomposite adsorbent via RAFT technique for the adsorption of toxic copper ions | |
| CN104119631B (en) | Preparation has the method for the temperature sensitive modified manometer silicon dioxide complex of different critical response temperature | |
| Graillot et al. | Removal of nickel ions from aqueous solution by low energy-consuming sorption process involving thermosensitive copolymers with phosphonic acid groups | |
| Wang et al. | Preparation of a novel TETA functionalized magnetic PGMA nano-absorbent by ATRP method and used for highly effective adsorption of Hg (II) | |
| Bai et al. | Stalagmites in karst cave inspired construction: lotus root-type adsorbent with porous surface derived from CO2-in-water Pickering emulsion for selective and ultrafast uranium extraction | |
| CN102992337A (en) | Functional attapulgite particle with amido on surface and preparation method thereof | |
| CN111318265A (en) | Preparation method and application of mosaic type magnetic imprinting adsorbent | |
| Wang et al. | Novel chitosan-based ions imprinted bio-adsorbent for enhanced adsorption of gallium (III) in acidic solution | |
| Li et al. | A thin shell and “sunny shape” molecular imprinted fluorescence sensor in selective detection of trace level pesticides in river | |
| Jiang et al. | Synthesis and property of poly (sodium 4-styrenesulfonate) grafted chitosan by nitroxide-mediated polymerization with chitosan-TEMPO macroinitiator | |
| Maneechakr et al. | Facile utilization of magnetic MnO2@ Fe3O4@ sulfonated carbon sphere for selective removal of hazardous Pb (II) ion with an excellent capacity: Adsorption behavior/isotherm/kinetic/thermodynamic studies | |
| Wang et al. | Preparation of wheat straw matrix-g-polyacrylonitrile-based adsorbent by SET-LRP and its applications for heavy metal ion removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150204 Termination date: 20201220 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |