CN103044640A - Attapulgite grafted polystyrene hybrid particle and preparation method thereof - Google Patents
Attapulgite grafted polystyrene hybrid particle and preparation method thereof Download PDFInfo
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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 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.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 is surface-modifying agent etc. and the existing group generation chemical reaction of surface of inorganic particles, and 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.
Polystyrene (PS) is a kind of exploitation important thermoplastics early, has the preferably transparency, chemical stability and weathering resistance.The PS molecular chain is grafted to the brilliant surface of the single rod of attapulgite, can obtains a kind of 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, so 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: polystyrene graft is to the preparation method of attapulgite, the method is utilized at attapulgite's surface chemical bonding primary amino, again with the 4-(diethylin) salicylic aldehyde forms stable schiff bases, introduce the aryl tertiary amine group in attapulgite's surface, utilize peroxidation phenyl-diformyl-aryl tertiary amine redox initiation system, cause styrene monomer in the attapulgite's surface graft polymerization, by chemical bonding with polystyrene graft to attapulgite, can significantly improve attapulgite and polymer phase capacitive, give full play to both performances.
Attapulgite grafted polystyrene hybrid particle of the present invention is to be grafted with polystyrene at attapulgite.
The percentage of grafting of the polystyrene of described hybrid particle is 25.68%.
Another object of the present invention is to provide a kind of preparation method of polystyrene graft attapulgite.This preparation method adopts solution system, and graft polymerization rates is fast, reacting balance safety; Simple to operate, easily go.
Attapulgite grafted polystyrene hybrid particle of the present invention, according to the following steps preparation:
(1) attapulgite acid activation: the nano level attapulgite is scattered in hydrogen ion concentration in the acid of 1mol/L take mass ratio 1:10-1:20, filters after 24 hours, be washed with distilled water to neutrality, vacuum-drying, grinding is sieved, and namely gets the acid activation attapulgite;
(2) acid activation attapulgite in the step (1) is scattered in organic solvent take mass ratio as 1:20-1:50, ultra-sonic dispersion 30-60min drips primary aminoalkoxysilanes, 80-140 ℃ of reaction 6-10h; Reaction removes by filter solvent after finishing, with absolute ethanol washing for several times, vacuum-drying, grinding is sieved, and namely gets the attapulgite of surface chemistry bonding primary amino;
(3) attapulgite with surface chemistry bonding primary amino in the step (2) disperses in the dehydrated alcohol, ultra-sonic dispersion 30-60min, add the 4-(diethylin) salicylic aldehyde and an amount of anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out upper strata suspension, remove by filter behind the solvent with washed with isopropyl alcohol for several times, vacuum-drying, pulverizing, grinding are sieved, and namely get the surperficial attapulgite with redox initiator activity with the aryl tertiary amine group;
(4) attapulgite of surface in the step (3) with the aryl tertiary amine group is dispersed in the 150ml toluene, ultra-sonic dispersion 30-60min, add vinylbenzene, logical nitrogen 30min removes the oxygen in the system, stirs and be warming up to 40-60 ℃, add peroxidation phenyl-diformyl initiator, reaction 8-12h, after product filtered with toluene wash and take out for to remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets attapulgite grafted polystyrene hybrid particle.
Wherein used acid is hydrochloric acid or dilute sulphuric acid in the step (1).
Wherein used organic solvent is toluene or dimethylbenzene in the step (2).
Wherein step (2) wherein used primary aminoalkoxysilanes be a kind of in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl methyldiethoxysilane, the γ-aminopropyl methyl dimethoxysilane, the mass ratio of its consumption and attapulgite is 1:1-1:2.
The wherein attapulgite of the surface bond primary amino described in the 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 the step (4) and solvent toluene should be controlled at 8%-15%.
Wherein used oil soluble organic peroxy initiator is a kind of in peroxidation phenyl-diformyl, dicumyl peroxide, the benzoyl peroxide tert-butyl ester in the step (4).Consumption is the 1%-4% of monomer mass.
Attapulgite grafted polystyrene 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 solution system, product postprocessing is simple and easy.
(3) according to " surperficial Inducing Graft Polymerization " principle, introduce the aryl tertiary amine group that can produce free radical in attapulgite's surface, consist of oxidation-reduction trigger system with the organic peroxy class initiator in the oil 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 PS begins to decompose 320 ℃, so 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 the formula
gBe percentage of grafting; 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 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, 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 attapulgite of surface chemistry bonding primary amino.
The attapulgite 1g that gets surface chemistry bonding primary amino is dispersed in the dehydrated alcohol, ultrasonic vibration 40min, add the 1.5g4-(diethylin) salicylic aldehyde, an amount of anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out suspension, removes by filter solvent, with washed with isopropyl alcohol for several times, vacuum-drying, grinding is sieved, and namely gets surperficial attapulgite particle with the aryl tertiary amine group.
Getting the 0.5g surface is dispersed in the 150ml toluene with the attapulgite of aryl tertiary amine group, ultra-sonic dispersion 50min, add 12g vinylbenzene, logical nitrogen 30min removes the oxygen in the system, stirs and be warming up to 40 ℃, add peroxidation phenyl-diformyl initiator, reaction 10h, after product filtered with toluene wash and take out for to remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets attapulgite grafted polystyrene hybrid particle.
Embodiment 2
The 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, 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-aminopropyl triethoxysilane, after dripping, be heated to 110 ℃, reaction 10h is after reaction finishes, desolventizing, vacuum-drying, grinding is sieved, and namely gets the attapulgite of surface chemistry bonding primary amino.
The attapulgite of getting 1g surface chemistry bonding primary amino is dispersed in the dehydrated alcohol, ultrasonic vibration 40min, add the 1g4-(diethylin) salicylic aldehyde, an amount of anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out suspension, removes by filter solvent, with washed with isopropyl alcohol for several times, vacuum-drying, grinding is sieved, and namely gets surperficial attapulgite particle with the aryl tertiary amine group.
Getting the 0.5g surface is dispersed in the 150ml toluene with the attapulgite of aryl tertiary amine group, ultra-sonic dispersion 35min, add 15g vinylbenzene, logical nitrogen 30min removes the oxygen in the system, stirs and be warming up to 45 ℃, add 0.6g peroxidation phenyl-diformyl initiator, reaction 8-12h, after product filtered with toluene wash and take out for to remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets attapulgite grafted polystyrene hybrid particle.
Embodiment 3
The 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, 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 the 8g γ-aminopropyl triethoxysilane, after dripping, be heated to 140 ℃, reaction 6h is after reaction finishes, desolventizing, vacuum-drying, grinding is sieved, and namely gets the attapulgite of surface chemistry bonding primary amino.
The attapulgite 1g that gets surface chemistry bonding primary amino is dispersed in the dehydrated alcohol, ultrasonic vibration 40min, add the 1.5g4-(diethylin) salicylic aldehyde, an amount of anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out suspension, removes by filter solvent, with washed with isopropyl alcohol for several times, vacuum-drying, grinding is sieved, and namely gets surperficial attapulgite particle with the aryl tertiary amine group.
Getting the 0.5g surface is dispersed in the 150ml toluene with the attapulgite of aryl tertiary amine group, ultra-sonic dispersion 40min, add 12g vinylbenzene, logical nitrogen 30min removes the oxygen in the system, stirs and be warming up to 55 ℃, add 0.24g dicumyl peroxide initiator, reaction 10h, after product filtered with toluene wash and take out for to remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets attapulgite grafted polystyrene hybrid particle.
Embodiment 4
The 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, 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 the 4g 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 attapulgite of surface chemistry bonding primary amino.
The attapulgite 1g that gets surface chemistry bonding primary amino is dispersed in the dehydrated alcohol, ultrasonic vibration 40min, add the 1g4-(diethylin) salicylic aldehyde, an amount of anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out suspension, removes by filter solvent, with washed with isopropyl alcohol for several times, vacuum-drying, grinding is sieved, and namely gets surperficial attapulgite particle with the aryl tertiary amine group.
Getting the 0.5g surface is dispersed in the 150ml toluene with the attapulgite of aryl tertiary amine group, ultra-sonic dispersion 60min, add 18g vinylbenzene, logical nitrogen 30min removes the oxygen in the system, stirs and be warming up to 40-60 ℃, add 0.18g dicumyl peroxide initiator, reaction 10h, after product filtered with toluene wash and take out for to remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets attapulgite grafted polystyrene hybrid particle.
Test one
Oleophylic test: select pure attapulgite, attapulgite grafted polystyrene hybrid particle adds an amount of toluene in the 100ml beaker, gets above-mentioned two kinds of particles on a small quantity, and ultrasonic vibration 30min again is than two kinds of dispersion of particles situations.
Lipophilicity
After ultrasonic concussion, pure attapulgite is deposited in the bottom in a large number, and is limpider, and the attapulgite of polystyrene graft is suspended in the toluene, and system is muddy.Illustrate that the surface tension that has increased attapulgite and polar solvent behind the surperficial grafted polystyrene has reduced surface polarity, hybrid particle has well lipophilicity.
By consulting literatures learns that by consulting pertinent literature PS begins to decompose as can be known near 320 ℃, end is decomposed in 500 ℃ of front and back, so adopt thermal weight loss (TG) method to measure the percentage of grafting of the surperficial PS of hybrid particle.Recording maximum percentage of grafting is 25.68%.
Claims (8)
- An attapulgite grafted polystyrene hybrid particle and the preparation method, it is characterized in that step is as follows:(1) attapulgite acid activation: the nano level attapulgite is scattered in hydrogen ion concentration in the acid of 1mol/L take mass ratio 1:10-1:20, filters after 24 hours, be washed with distilled water to neutrality, vacuum-drying, grinding is sieved, and namely gets the acid activation attapulgite;(2) acid activation attapulgite in the step (1) is scattered in organic solvent take mass ratio as 1:20-1:50, ultra-sonic dispersion 30-60min drips primary aminoalkoxysilanes, 80-140 ℃ of reaction 6-10h; Reaction removes by filter solvent after finishing, with absolute ethanol washing for several times, vacuum-drying, grinding is sieved, and namely gets the attapulgite of surface chemistry bonding primary amino;(3) attapulgite with surface chemistry bonding primary amino in the step (2) disperses in the dehydrated alcohol, ultra-sonic dispersion 30-60min, add the 4-(diethylin) salicylic aldehyde and an amount of anhydrous sodium sulphate, stirring and refluxing 12h hypsokinesis goes out upper strata suspension, remove by filter behind the solvent with washed with isopropyl alcohol for several times, vacuum-drying, pulverizing, grinding are sieved, and namely get the surperficial attapulgite with redox initiator activity with the aryl tertiary amine group;(4) attapulgite of surface in the step (3) with the aryl tertiary amine group is dispersed in the 150ml toluene, ultra-sonic dispersion 30-60min, add vinylbenzene, logical nitrogen 30min removes the oxygen in the system, stirs and be warming up to 40-60 ℃, add peroxidation phenyl-diformyl initiator, reaction 8-12h, after product filtered with toluene wash and take out for to remove the polymkeric substance of surface adsorption, vacuum-drying, grinding is sieved, and namely gets the attapulgite hybrid particle of polystyrene graft.
- 2. the preparation method of a kind of attapulgite grafted polystyrene hybrid particle according to claim 1, it 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 a kind of 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 a kind of in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl methyldiethoxysilane, the γ-aminopropyl methyl 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, it 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, it 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, it is characterized in that: the mass ratio of described styrene monomer and solvent toluene should be controlled at 8%-15%.
- 7. an attapulgite grafted polystyrene hybrid particle is characterized in that, is grafted with polystyrene at attapulgite.
- 8. the percentage of grafting of the polystyrene of described hybrid particle is 25.68%.
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Cited By (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 |
| CN109232817A (en) * | 2018-09-28 | 2019-01-18 | 常州大学 | A kind of preparation method of in situ reactive 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 |
| WO2020027735A1 (en) * | 2018-07-30 | 2020-02-06 | Agency For Science, Technology And Research | Silane grafted onto clay |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247807A (en) * | 2011-05-17 | 2011-11-23 | 江苏麦阁吸附剂有限公司 | Preparation method and usage of modified attapulgite adsorption material |
| CN102558461A (en) * | 2011-08-15 | 2012-07-11 | 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 |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247807A (en) * | 2011-05-17 | 2011-11-23 | 江苏麦阁吸附剂有限公司 | Preparation method and usage of modified attapulgite adsorption material |
| CN102558461A (en) * | 2011-08-15 | 2012-07-11 | 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 |
Cited By (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 |
| CN109232817A (en) * | 2018-09-28 | 2019-01-18 | 常州大学 | A kind of preparation method of in situ reactive 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 |
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