CN103012699A - Attapulgite grafted polymethyl methacrylate hybrid particle and preparation method thereof - Google Patents
Attapulgite grafted polymethyl methacrylate hybrid particle and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an attapulgite grafted polymethyl methacrylate hybrid particle and a preparation method thereof, and provides a hybrid particle which is prepared by taking methyl methacrylate and attapulgite clay as main raw materials, high in grafting rate and subjected to organic-inorganic connection by using chemical bonds. According to the invention, in accordance with a 'surface induced grafting' principle, an oxidation-reduction initiating system is formed by using attapulgite with amino and peroxydisulfate particles in aqueous phases, so that a graft polymerization reaction occurs on the surface of attapulgite, and then the attapulgite grafted polymethyl methacrylate hybrid particle is prepared. The preparation method of the hybrid particle, disclosed by the invention, is a soap-free emulsion method which can prevent the homopolymerization and reaction of monomers in low-polymer micelles in aqueous phases to the maximum extent, so that the monomers mainly take attapulgite particles as initial micelles for carrying out surface graft polymerization reaction. The polymer grafting rate of the prepared attapulgite grafted polymethyl methacrylate hybrid particle can reach 29.36%.
Description
Technical field
The present invention relates to a kind of attapulgite grafting polymethyl methacrylate hybrid particle and preparation method thereof.
Background technology
Attapulgite clay is a kind of manosil AS salt mine that contains Shuifu County's magnesium with specialty fibers shape crystal habit structure take Attapulgite as main component.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, basic structure is divided into three levels.The one, the thickness length of brilliant bundle.Because rod is brilliant the tightst in the intrafascicular gathering of crystalline substance, therefore, brilliant bundle ratio more tiny or tiny brilliant Shu Suozhan is larger, and then the microstructure of recessed soil is just looser, and vice versa.The 2nd, the state of aggregation of brilliant bundle.If brilliant interfascicular is parallel tight gathering more, then microstructure is just fine and close.Otherwise if brilliant bundle is loose staggered arrangement at three-dimensional space, then brilliant interfascicular interval is large, and microstructure is just loose.The 3rd, whether be formed with built on stilts hole, crack etc. in the microstructure.If then microstructure is just loose.In order to improve the effective deployment conditions of attapulgite in polymeric matrix, usually it is carried out suitable modification.Method of modifying commonly used mainly is divided into physically modified and chemical modification.Physically modified mainly is adsorbed on nanoparticle surface by reactive force between Van der Waals force, hydrogen bond force equimolecular with organic modifiers, form coating layer on the surface, thereby reduction surface tension, reduce the reunion between nanoparticle, reach the purpose of uniform and stable dispersion, so this method is called again the modification of absorption parcel.Chemical modification be surface-modifying agent etc. with surface of inorganic particles write group generation chemical reaction, properties-correcting agent etc. are received particle surface with chemical bond-linking, to reach the purpose 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.But the surface grafting polymerization method is mainly utilized the attapulgite's surface reactive group, adopt its silane coupling agent that but polymerizable double bond or initiating activity point are introduced in its modification, as: prepare attapulgite-water-borne polyurethane nano composite leather coating agent (publication number: CN101565588, a kind of organic attapulgite soil-water-borne polyurethane nano composite leather coating agent and preparation method thereof) by situ aggregation method behind the employing attapulgite modified by silane coupling agent such as Lin Wei; The vinylformic acid of the employings such as Wang Aiqin part neutralization 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) in the presence of initiator.
Polymethylmethacrylate (PMMA) is a kind of exploitation important thermoplastics early, has the preferably transparency, chemical stability and weathering resistance, and different dyeing, easily processing, outward appearance is graceful, has kind to use widely in construction industry.The PMMA molecular chain is grafted to the brilliant surface of the single rod of attapulgite, can obtains a kind of blank particle of hybrid material, and effectively improve the brilliant agglomeration in polymkeric substance of attapulgite rod, realize that nano level disperses.
Adopt attapulgite to prepare the advantage that compound ability two can be given full play to both performances as inorganic phase, have simultaneously the reduction cost, effectively utilize the economic benefit of attapulgite natural nano-material.Sun Hongxiu, the people such as Zhuan Wei adopt the in-situ suspension polymerization legal system for acrylate copolymer/attapulgite composite material, adopt the soap-free emulsion legal system for poly-methylpropanoic acid methyl esters/attapulgite modified complex microsphere, and studied the performance (preparation and property of the acrylate copolymer/organic-silicon-modified attapulgite composite material research of matrix material, plastics industry, the 9th phase in 2011; The standby polymethylmethacrylate of soap-free emulsion legal system/attapulgite modified microballoon and performance study thereof, Speciality Petrochemicals, the 5th phase in 2011).
Aforesaid method mainly is to adopt 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 the mechanical blending method, but because 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, can't form effective hybridization network structure, the poor dispersion of attapulgite in polymerization, easily assemble, utilization ratio is not high, can not be 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: polymethylmethacrylate is grafted to the preparation method of attapulgite, the method is utilized at attapulgite's surface chemical anchoring active amino, consist of oxidation-reduction trigger system with the persulfate ion, cause the attapulgite's surface graft polymerization, mode by the extensive chemical bonding is grafted to polymethylmethacrylate on the attapulgite, can significantly improve the binding strength of attapulgite and polymkeric substance, and percentage of grafting is high, can give full play to both performances.
Attapulgite grafting polymethyl methacrylate hybrid particle of the present invention, its structure is to be grafted with polymethylmethacrylate at attapulgite.
Another object of the present invention is to provide the preparation method of polymethylmethacrylate grafting attapulgite.This preparation method adopts the soap-free emulsion system, and graft polymerization rates is fast, and the side reactions such as monomer homopolymerization are few; Take water as medium, reaction heat is easily derived, reacting balance safety; Simple to operate, easily go.
For finishing the foregoing invention purpose, carry out according to the following steps:
(1) pre-treatment of attapulgite: the attapulgite powder that will contain impurity is scattered in the water take the solid-liquid mass ratio as 1:10-1:30, add Sodium hexametaphosphate 99, wherein hexa metaphosphoric acid is the 1%-5% of attapulgite powder quality, 50-80 ℃ is stirred after 4-6 hour upper strata suspension inclined and filtration, with distilled water wash for several times, vacuum-drying, grinding is sieved, and namely gets the purifying attapulgite.
(2) attapulgite acid activation: above-mentioned purifying attapulgite is scattered in hydrogen ion concentration in the acid of 1mol/L take mass ratio 1:10-1:20, filter after 24 hours, be washed with distilled water to neutrality, vacuum-drying, grinding is sieved, and namely gets the acid activation attapulgite.
(3) acid activation attapulgite in the step (2) is scattered in organic solvent take mass ratio as 1:20-1:50, ultra-sonic dispersion 30-60min drips aminoalkoxy silane, 80-140 ℃ of reaction 6-10h; After finishing, reaction removes by filter solvent, with absolute ethanol washing for several times, vacuum-drying, grinding is sieved, and namely gets surperficial attapulgite modified with amino.
(4) the silane-modified attapulgite of aminoalkoxy in the step (3) is dispersed in the methyl methacrylate monomer, ultra-sonic dispersion 5-10min, add 100-200ml distilled water, logical nitrogen 30min removes the oxygen in the system, stirring also is warming up to 55-65 ℃, add persulfate initiator, reaction 8-12h, filter after adding the saturated aqueous common salt breakdown of emulsion, fully wash with tetrahydrofuran (THF), remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets attapulgite grafting polymethyl methacrylate hybrid particle.
Wherein used acid is hydrochloric acid or dilute sulphuric acid in the step (2).
Wherein used organic solvent is toluene or dimethylbenzene in the step (3).
Wherein used aminoalkoxy silane is in the step (3): a kind of in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, γ-aminopropyl methyldiethoxysilane, the γ-aminopropyl methyl dimethoxysilane, wherein the mass ratio of aminoalkoxy silane and attapulgite is 1:1-1:2.
Wherein the silane-modified attapulgite of aminoalkoxy described in the step (4) and methyl methacrylate monomer mass ratio are 1:20-1:50.
Wherein used persulfate initiator is a kind of in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate in the step (4).Initiator amount is the 0.5%-1.5% of monomer mass.
As shown from the above technical solution: the present invention at first introduces amino by aminoalkoxy silane in attapulgite's surface; Then consist of redox initiation system by the persulfate particle in amino and the solution, Methyl Methacrylate is at the attapulgite's surface graft polymerization reaction, thus the chemical bonding of realization attapulgite and polymethylmethacrylate.
Attapulgite grafting polymethyl methacrylate hybrid particle preparation method's of the present invention advantage is:
(1) adopt oxidation-reduction trigger system, temperature of reaction is low, and heat radiation easily, and is simple to operate.
(2) adopt the soap-free emulsion system, reduced to the full extent the formation of aqueous phase oligomer micelle, increased the per-cent that participates in the graft polymerization reaction monomer.
(3) according to " surperficial initiation grafting " principle, introduce the active amino that can produce free radical in attapulgite's surface, consist of oxidation-reduction trigger system with the persulfate particle of aqueous phase, graft polymerization reaction is occured in attapulgite's surface, overcome the low defective of situ aggregation method percentage of grafting; Simultaneously, also avoided the drawback of the initiator group activity decreased introduced at particle surface in " surperficial Inducing Graft Polymerization " reaction.
Near the calculating of percentage of grafting: learn that by consulting pertinent literature PMMA begins to decompose 270 ℃, therefore adopt thermal weight loss (TG) method to measure the percentage of grafting of hybrid particle surface PMMA.Be calculated as follows percentage of grafting (γ
g)
γ in the formula
gBe percentage of grafting, g/g; m
1: the quality of graft product; m
2: the quality of the polymkeric substance of grafting.
Embodiment
Employed term among the present invention unless other explanation is arranged, 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 embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way
Embodiment 1
The impure attapulgite of 10g is scattered in the 100mL distilled water, and ultra-sonic dispersion 60min adds the 0.2g Sodium hexametaphosphate 99, is heated to 70 ℃, stirs the 4h hypsokinesis and goes out upper strata suspension, and desolventizing, washing for several times final vacuum are dry, and grinding is sieved, and namely gets the purifying attapulgite.
The purifying attapulgite is dispersed in ultrasonic vibration 6 in the hydrochloric acid of 1mol/L, removes solvent after leaving standstill 24h, washing is to neutral, vacuum-drying, and grinding is sieved, and namely gets the acid activation attapulgite.
Getting 4g acid activation attapulgite soil is scattered in the 100mL toluene, ultra-sonic dispersion 60min under the agitation condition, drips the 8g γ-aminopropyl triethoxysilane, after dripping, be heated to 80 ℃, reaction 12h is after reaction finishes, desolventizing, vacuum-drying, grinding is sieved, and namely gets the silane-modified organic attapulgite soil of aminoalkoxy.
Get in the attapulgite modified 5g of the being dispersed in methyl methacrylate monomer of 0.5g amino coupling agent, ultrasonic vibration 5min adds 100ml distilled water, logical nitrogen 30min, remove the oxygen in the system, be warming up to 60 ℃, add the 0.05g initiator ammonium persulfate, behind the reaction 10h, add saturated aqueous common salt, filter behind the system layering, final vacuum is dry for several times with the tetrahydrofuran (THF) washing with product, grinding is sieved, and namely gets attapulgite grafting polymethyl methacrylate hybrid particle.
Embodiment 2
The impure attapulgite of 10g is scattered in the 200mL distilled water, and ultra-sonic dispersion 30min adds the 0.2g Sodium hexametaphosphate 99, is heated to 80 ℃, stirs the 6h hypsokinesis and goes out upper strata suspension, and desolventizing, washing for several times final vacuum are dry, and grinding is sieved, and namely gets the purifying attapulgite.
The purifying 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, vacuum-drying, and grinding is sieved, and namely gets the acid activation attapulgite.
Getting 4g acid activation attapulgite soil is scattered in the 150mL toluene, ultra-sonic dispersion 30min under the agitation condition, drips the 4g γ-aminopropyltrimethoxysilane, after dripping, be heated to 110 ℃, reaction 10h is after reaction finishes, desolventizing, vacuum-drying, grinding is sieved, and namely gets the silane-modified organic attapulgite soil of aminoalkoxy.
Go in the attapulgite modified 7g of the being dispersed in methyl methacrylate monomer of 0.5g amino coupling agent, ultrasonic vibration 10min adds 100ml distilled water, logical nitrogen 30min, remove the oxygen in the system, be warming up to 65 ℃, add the 0.1g initiator ammonium persulfate, behind the reaction 10h, add saturated aqueous common salt, filter behind the system layering, final vacuum is dry for several times with the tetrahydrofuran (THF) washing with product, grinding is sieved, and namely gets attapulgite grafting polymethyl methacrylate hybrid particle.
Embodiment 3
The impure attapulgite of 10g is scattered in the 250mL distilled water, and ultra-sonic dispersion 40min adds the 0.1g Sodium hexametaphosphate 99, is heated to 60 ℃, stirs the 5h hypsokinesis and goes out upper strata suspension, and desolventizing, washing for several times final vacuum are dry, and grinding is sieved, and namely gets the purifying attapulgite.
The purifying attapulgite is dispersed in ultrasonic vibration 40min in the hydrochloric acid of 1mol/L, removes solvent after leaving standstill 24h, washing is to neutral, vacuum-drying, and grinding is sieved, and namely gets the acid activation attapulgite.
Getting 4g acid activation attapulgite soil is scattered in the 100mL dimethylbenzene, ultra-sonic dispersion 40min under the agitation condition, drips 8g N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, after dripping, be heated to 140 ℃, reaction 6h is after reaction finishes, desolventizing, vacuum-drying, grinding is sieved, and namely gets the silane-modified organic attapulgite soil of aminoalkoxy.
Go in the attapulgite modified 8g of the being dispersed in methyl methacrylate monomer of 0.5g amino coupling agent, ultrasonic vibration 10min adds 150ml distilled water, logical nitrogen 30min, remove the oxygen in the system, be warming up to 55 ℃, add the 0.05g initiator ammonium persulfate, behind the reaction 10h, add saturated aqueous common salt, filter behind the system layering, final vacuum is dry for several times with the tetrahydrofuran (THF) washing with product, grinding is sieved, and namely gets attapulgite grafting polymethyl methacrylate hybrid particle.
Embodiment 4
The impure attapulgite of 10g is scattered in the 300mL distilled water, and ultra-sonic dispersion 50min adds the 0.15g Sodium hexametaphosphate 99, be heated to 50 ℃, stir the 5h hypsokinesis and go out upper strata suspension, desolventizing, washing for several times final vacuum is dry, and grinding is sieved, and namely gets the purifying attapulgite.
The purifying attapulgite is dispersed in ultrasonic vibration 50min in the hydrochloric acid of 1mol/L, removes solvent after leaving standstill 24h, washing is to neutral, vacuum-drying, and grinding is sieved, and namely gets the acid activation attapulgite.
Getting 4g acid activation attapulgite soil is scattered in the 150mL dimethylbenzene, ultra-sonic dispersion 50min under the agitation condition, drips 4gN-(β-aminoethyl)-γ-aminopropyl triethoxysilane, after dripping, be heated to 140 ℃, reaction 8h is after reaction finishes, desolventizing, vacuum-drying, grinding is sieved, and namely gets the silane-modified organic attapulgite soil of aminoalkoxy.
Go in the attapulgite modified 10g of the being dispersed in methyl methacrylate monomer of 0.5g amino coupling agent, ultrasonic vibration 10min adds 200ml distilled water, logical nitrogen 30min, remove the oxygen in the system, be warming up to 50 ℃, add the 0.08g initiator ammonium persulfate, behind the reaction 10h, add saturated aqueous common salt, filter behind the system layering, final vacuum is dry for several times with the tetrahydrofuran (THF) washing with product, grinding is sieved, and namely gets attapulgite grafting polymethyl methacrylate hybrid particle.
Test one
Hydrophilic test: select pure attapulgite, attapulgite grafting polymethyl methacrylate hybrid particle, in the 100ml beaker, add an amount of distilled water, get above-mentioned two kinds of particles a small amount of, join and observe the dispersion of particles situation in the beaker, ultrasonic vibration 30min again, the two kinds of dispersion of particles situations in more ultrasonic front and back.
Wetting ability
Pure attapulgite is added to the water and gets started by sinking, and on the attapulgite of polymethylmethacrylate grafting is bubbled through the water column, and do not sink after the slight wobble.After ultrasonic concussion, pure attapulgite is suspended in the water in a large number, and system is muddy, and the attapulgite of polymethylmethacrylate grafting is as for being suspended on a small quantity in the water, and water is slightly muddy, but a large amount of hybrid particle is still bubbled through the water column.The surface tension that has increased attapulgite and polar solvent behind the surface grafting polymethylmethacrylate is described, hybrid particle has very large hydrophobicity.
Test two
The percentage of grafting of attapulgite grafting polymethyl methacrylate hybrid particle is measured, By consulting literatures learns that by consulting pertinent literature polymethylmethacrylate begins to decompose as can be known near 270 ℃, therefore adopt thermal weight loss (TG) method to measure the percentage of grafting of hybrid particle surface polymethylmethacrylate.
Claims (8)
1. the preparation method of an attapulgite grafting polymethyl methacrylate hybrid particle is characterized in that preparation process is as follows:
(1) pre-treatment of attapulgite: the attapulgite clay powder is scattered in the water take the solid-liquid mass ratio as 1:10-1:30, add Sodium hexametaphosphate 99, wherein hexa metaphosphoric acid is the 1%-5% of attapulgite clay powder quality, 50-80 ℃ is stirred after 4-6 hour upper strata suspension inclined and filtration, with distilled water wash for several times, vacuum-drying, grinding is sieved, and namely gets the purifying attapulgite;
(2) attapulgite acid activation: above-mentioned purifying attapulgite is scattered in hydrogen ion concentration in the acid of 1mol/L take mass ratio 1:10-1:20, filter after 24 hours, be washed with distilled water to neutrality, vacuum-drying, grinding is sieved, and namely gets the acid activation attapulgite;
(3) acid activation attapulgite in the step (2) is scattered in organic solvent take mass ratio as 1:20-1:50, ultra-sonic dispersion 30-60min drips aminoalkoxy silane, 80-140 ℃ of reaction 6-10h; After finishing, reaction removes by filter solvent, with absolute ethanol washing for several times, vacuum-drying, grinding is sieved, and namely gets surperficial attapulgite modified with amino;
(4) the silane-modified attapulgite of aminoalkoxy in the step (3) is dispersed in the methyl methacrylate monomer, ultra-sonic dispersion 5-10min, add 100-200ml distilled water, logical nitrogen 30min removes the oxygen in the system, stirring also is warming up to 55-65 ℃, add persulfate initiator, reaction 8-12h, filter after adding the saturated aqueous common salt breakdown of emulsion, fully wash with tetrahydrofuran (THF), remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets attapulgite grafting polymethyl methacrylate hybrid particle.
2. the preparation method of a kind of attapulgite grafting polymethyl methacrylate hybrid particle according to claim 1, it is characterized in that: described organic solvent is toluene or dimethylbenzene; Described aminoalkoxy silane is a kind of in γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, γ-aminopropyl methyldiethoxysilane, the γ-aminopropyl methyl dimethoxysilane.
3. the preparation method of a kind of attapulgite grafting polymethyl methacrylate hybrid particle according to claim 1, it is characterized in that: the percentage of grafting of the polymethylmethacrylate of described hybrid particle is 29.36%.
4. the preparation method of a kind of attapulgite grafting polymethyl methacrylate hybrid particle according to claim 1, it is characterized in that: the mass ratio of described aminoalkoxy silane consumption and attapulgite is 1:1-1:2.
5. the preparation method of a kind of attapulgite grafting polymethyl methacrylate hybrid particle according to claim 1, it is characterized in that: described initiator amount is the 0.5%-1.5% of monomer mass.
6. the preparation method of a kind of attapulgite grafting polymethyl methacrylate hybrid particle according to claim 1, it is characterized in that: the mass ratio of the silane-modified attapulgite of described aminoalkoxy and methyl methacrylate monomer is 1:20-1:50.
7. an attapulgite grafting polymethyl methacrylate hybrid particle is characterized in that, is grafted with polymethylmethacrylate on the attapulgite.
8. attapulgite grafting polymethyl methacrylate hybrid particle according to claim 7 is characterized in that by following method preparation:
(1) pre-treatment of attapulgite: the attapulgite clay powder is scattered in the water take the solid-liquid mass ratio as 1:10-1:30, add Sodium hexametaphosphate 99, wherein hexa metaphosphoric acid is the 1%-5% of attapulgite clay powder quality, 50-80 ℃ is stirred after 4-6 hour upper strata suspension inclined and filtration, with distilled water wash for several times, vacuum-drying, grinding is sieved, and namely gets the purifying attapulgite;
(2) attapulgite acid activation: above-mentioned purifying attapulgite is scattered in hydrogen ion concentration in the acid of 1mol/L take mass ratio 1:10-1:20, filter after 24 hours, be washed with distilled water to neutrality, vacuum-drying, grinding is sieved, and namely gets the acid activation attapulgite;
(3) acid activation attapulgite in the step (2) is scattered in organic solvent take mass ratio as 1:20-1:50, ultra-sonic dispersion 30-60min drips aminoalkoxy silane, 80-140 ℃ of reaction 6-10h; After finishing, reaction removes by filter solvent, with absolute ethanol washing for several times, vacuum-drying, grinding is sieved, and namely gets surperficial attapulgite modified with amino;
(4) the silane-modified attapulgite of aminoalkoxy in the step (3) is dispersed in the methyl methacrylate monomer, ultra-sonic dispersion 5-10min, add 100-200ml distilled water, logical nitrogen 30min removes the oxygen in the system, stirring also is warming up to 55-65 ℃, add persulfate initiator, reaction 8-12h, filter after adding the saturated aqueous common salt breakdown of emulsion, fully wash with tetrahydrofuran (THF), remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets attapulgite grafting polymethyl methacrylate hybrid particle.
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