CN101058682A - Method of preparing aromatic diamine modified nano concavo-convex stick - Google Patents
Method of preparing aromatic diamine modified nano concavo-convex stick Download PDFInfo
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- CN101058682A CN101058682A CN 200710040487 CN200710040487A CN101058682A CN 101058682 A CN101058682 A CN 101058682A CN 200710040487 CN200710040487 CN 200710040487 CN 200710040487 A CN200710040487 A CN 200710040487A CN 101058682 A CN101058682 A CN 101058682A
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- attapulgite
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Abstract
The invention discloses a method preparing for an aromatic diamine modifying nanometer concave-convex stick relating to a nanometer material technique field, which comprises the following steps: dispersing the nanometer concave-convex stick sufficiently in the quantitative solvent; adding the excess methyl diphenylene diisocyanate in the condition of the nitrogen protection and mixing; getting the nanometer concave-convex stick with the isocyanate group on the surface after the complement of the reaction; reacting between aromatic diamine and the concave-convex stick with the isocyanate group on the surface; washing sufficiently after the end of the reaction; getting aromatic diamine modifying nanometer concave-convex stick after drying. The invention improves the stability of the colloid in the organic solvent, which improves the organic content of the concave-convex stick; has a high property.
Description
Technical field
The invention belongs to the material material technology field of receiving, be specifically related to a kind of finishing that is used for the nano-attapulgite of polymer nanocomposites.
Background technology
Along with the development of nanotechnology, polymer nanocomposites has become the focus of research in recent years.Usually add calorifics and the mechanical property that very a spot of nano particle just can greatly improve polymer materials.But owing to have very big surface energy, nanoparticle is gathered into larger particles easily, and consistency is relatively poor between the polymeric matrix.Therefore, nanoparticle surface is carried out the basis that chemically modified is the preparation high performance composite.
In the nano material of various different shapes, specific surface area is big, length-to-diameter ratio is high owing to having for monodimension nanometer material, is subjected to paying close attention to widely.Attapulgite is a kind of natural rod-like clay particle, and it has splendid thermostability and mechanical property, and it is brilliant to be easy to be dispersed into single rod, wide material sources and cheap.There have been a lot of research work that Attapulgite is come reinforced polymeric material as Nano filling at present.But, limited it in the polymer nanocomposites Application for Field because the Attapulgite surface hydrophilic is relatively poor with the consistency of polymkeric substance.The surface chemical modification of Attapulgite is to changing its hydrophilic surface properties, promoting that the brilliant interfacial interaction of peeling off and strengthening between Attapulgite and the polymkeric substance of rod is all significant.At present the finishing of Attapulgite is mainly undertaken by coupling agent or ion-exchange techniques, usually reaction efficiency is lower, bonding force a little less than.Therefore, press for the method for a kind of reaction efficiency height, strong, the regulatable Attapulgite finishing of bonding force.
Summary of the invention
The object of the present invention is to provide a kind of efficiently, controllably organically-modified method is carried out on the surface of nano-attapulgite.
The present invention introduces active group on Attapulgite surface, change the surface properties of the hydrophilic oleophobic of nano-attapulgite, and then strengthens the consistency between itself and organic phase.Obviously improve through the colloidal stability of Attapulgite in organic solvent after aromatic diamine modified, and can introduce covalent bonding, polymkeric substance is played tangible reinforced effects by being reflected between Attapulgite and polymkeric substance of amido and other organic groups.
The preparation method of the aromatic diamine modified nano-attapulgite that the present invention proposes, its response path is as follows:
Above-mentioned path may further comprise the steps:
Step 1: will be dispersed in then in the organic solvent through vacuum drying nano-attapulgite, adopt high-shear emulsion machine and ultrasonoscope to make the Attapulgite homodisperse, obtaining massfraction is the nano-attapulgite suspension of 5-10%; This suspension is transferred in the there-necked flask that whipping appts, return line and airway are housed, leads to after rare gas element 12-15 minute, add excessive diphenylmethanediisocyanate, reacted 60-120 minute down in 60-80 ℃ of noble gas protection.
Step 2: the mixed solution that above-mentioned steps 1 obtains is centrifugal, and obtain the nano-attapulgite that the surface has isocyanate groups with organic solvent washing, with centrifugal products therefrom redispersion in organic solvent, make the nano-attapulgite homodisperse with high-shear emulsion machine, obtain the suspension that massfraction is 5-10%.Under the situation of stirring and logical rare gas element, in this suspension, add 4, the dimethyl formamide solution of 4 '-diamines yl diphenyl ether.Reacted 10-15 hour down in 50-60 ℃ of protection of inert gas, in the mixed solution, the mass ratio of 4,4 '-diamines yl diphenyl ether and nano-attapulgite is 0.5: 1-2: 1.After reaction finishes, with suspension in centrifugal, and successively with dimethyl formamide, deionized water, washing with acetone to remove unreacted small molecules.To grind after the vacuum-drying of gained solid, sieve, promptly obtain the Attapulgite that surperficial amido is modified.
In the preparation process of the present invention, the massfraction of nano-attapulgite is about 5-10% in the suspension of nano-attapulgite.The diameter of nano-attapulgite is the 20-50 nanometer, and length is 500 nanometers to 2 micron.
Used organic solvent is following any in the preparation process of the present invention: acetone, dimethyl formamide.To remove water treatment as the organic solvent use is last.
Reaction process of the present invention should be led to rare gas element such as nitrogen etc. and protected.
In the preparation process of the present invention active intermediate product and aromatic diamine modified nano-attapulgite are carried out centrifugation, adopt supercentrifuge, centrifuge speed is 4000-8000r/min.
Compare with not modified Attapulgite, and increased 2275cm newly in the infrared spectrum of Attapulgite behind the di-isocyanate reaction
-1Bands of a spectrum are characteristic peaks of isocyanate groups.1648cm appears respectively in acid amides absorption band I and II
-1And 1544cm
-1, show that between the hydroxyl on vulcabond and Attapulgite surface chemical reaction having taken place has been grafted to the Attapulgite surface.After the aromatic diamine reaction, 2275cm
-1The isocyanic ester at place has absorbed completely dissolve, and the intensity of acid amides absorption band strengthens to some extent, and the isocyanic ester that shows the Attapulgite surface is by transforming for amido with reacting completely of aromatic diamine.
Organic content can reach more than the 25wt%, as shown in Figure 3 in the aromatic diamine modified Attapulgite of employing the present invention preparation.The Attapulgite of finishing has higher heat decomposition temperature, and its temperature of initial decomposition is about 290 ℃.
The colloidal stability of Attapulgite in dimethyl formamide as shown in Figure 4 before and after amido was modified, can see, the colloidal stability of aromatic diamine modified attapulgite in organic solvent obviously improves, and shows that the consistency between attapulgite and the organic phase improves.
Adopt the aromatic diamine modified nano-attapulgite of the inventive method preparation, its advantage is:
1, preparation process is simple and easy to do.
2, graft reaction efficient height, organic content can reach more than 25% in the nano-attapulgite after treatment usually, can play the effect of stable dispersion, has higher thermostability simultaneously.
3, the amido on the Attapulgite surface of finishing has the certain reaction activity, can react polymkeric substance/Attapulgite nano composite material that the preparation covalent linkage connects with the polymer chain that contains group such as acid anhydrides.
Description of drawings
Fig. 1 is the electron scanning micrograph before and after the Attapulgite finishing, can see that surface treatment does not change the bar-shaped form of nano-attapulgite, and its diameter is about the 20-50 nanometer, is about the hundreds of nanometer to several microns.
A among Fig. 2, b, c spectral line are respectively the infrared spectras of the attapulgite of nano-attapulgite, reaction intermediate, finishing.
A, b two curves are respectively the thermogravimetric curve of nano-attapulgite in nitrogen before and after the finishing among Fig. 3.
Shown in Figure 4 is Attapulgite and 4, the colloidal stability of nano-attapulgite in the dimethyl formamide evolutionary process in time that 4 '-diamines yl diphenyl ether is modified.
Embodiment
Embodiment 1: nano-attapulgite 140-160 ℃ of vacuum-drying more than 12 hours.The 5g Concavo-convex stick after purifying is dispersed in the 75g anhydrous dimethyl formamide, and high-shear emulsion machine was disperseed 50-70 minute, made the suspension of Attapulgite in ultra-sonic dispersion 50-70 minute.Get 2.502g 4,4 '-diphenylmethanediisocyanate is dissolved in the 20g dry DMF, joins gradually in the suspension of above-mentioned attapulgite clay under the condition of logical nitrogen.This mixed solution is at 80 ℃ of following nitrogen protection back flow reaction 1h.After reaction finishes, with behind twice of the anhydrous dimethyl formamide centrifuge washing with the reaction intermediate redispersion in the 100g anhydrous dimethyl formamide.This suspension is heated to 55 ℃, in this suspension, adds 4g 4,4 '-diamines yl diphenyl ether.Stirring reaction spends the night under the nitrogen protection.After reaction finishes, mixed solution is centrifugal in the 6000r/min rotating speed, use anhydrous dimethyl formamide, deionized water, washing with acetone successively once.The aromatic diamine modified Attapulgite of gained is in 80 ℃ of following dryings of vacuum drying oven 24h at least.
Embodiment 2: 10g is dispersed in the 70g anhydrous dimethyl formamide through vacuum drying nano-attapulgite; high-shear emulsion machine is disperseed 1h; ultra-sonic dispersion 1h. takes by weighing 5.004g 4; 4 '-diphenylmethanediisocyanate is dissolved in the 20g anhydrous dimethyl formamide, joins gradually in the suspension of above-mentioned Attapulgite under nitrogen protection.The gained mixed solution is at 80 ℃ of following nitrogen protection back flow reaction 1h.After reaction finishes, behind twice of the anhydrous dimethyl formamide centrifuge washing, with the reaction intermediate redispersion in the 100g anhydrous dimethyl formamide.This suspension is heated to 60 ℃, in this suspension, adds 16g 4,4 '-diamines yl diphenyl ether.Stirring reaction spends the night under the nitrogen protection.After reaction finishes, mixed solution is centrifugal in the 8000r/min rotating speed, use anhydrous dimethyl formamide, deionized water, washing with acetone successively once.The aromatic diamine modified attapulgite of gained is in 80 ℃ of following dryings of vacuum drying oven 24h at least.
The colloidal stability of the nano-attapulgite for preparing in the above-mentioned example in organic solvent obviously improves, and sees shown in Figure 4.And the consistency between polymkeric substance obviously strengthens, thereby can be used for preparing polymkeric substance/Attapulgite nano composite material.
Claims (4)
1. the preparation method of an aromatic diamine modified nano-attapulgite is characterized in that concrete steps are as follows:
Step 1: will be dispersed in the organic solvent through vacuum drying nano-attapulgite, adopt high-shear emulsion machine and ultrasonoscope to make the nano-attapulgite homodisperse, making massfraction is the nano-attapulgite suspension of 5-10%; This suspension is transferred in the there-necked flask that whipping appts, return line and airway are housed, logical rare gas element 12-15 minute, add excessive diphenylmethanediisocyanate again, reacted 60-120 minute down in 60-80 ℃ of protection of inert gas;
Step 2: the mixed solution that above-mentioned steps 1 obtains is centrifugal, and use organic solvent washing, obtain the nano-attapulgite that the surface has isocyanate groups; Centrifugal products therefrom redispersion in organic solvent, is made the nano-attapulgite homodisperse with high-shear emulsion machine, obtain the suspension that massfraction is 5-10%; Under the situation of stirring and logical rare gas element, in this suspension, add 4, the dimethyl formamide solution of 4 '-diamines yl diphenyl ether, reacted 10-15 hour down in 50-60 ℃ of protection of inert gas, in the mixed solution, 4, the mass ratio of 4 '-diamines yl diphenyl ether and nano-attapulgite is 0.5: 1-2: 1; After reaction finishes, suspension is centrifugal, and successively with dimethyl formamide, deionized water, washing with acetone to remove unreacted small molecules, will grind after the vacuum-drying of gained solid, sieve, promptly obtain the Attapulgite of surperficial amido modification.
2, the preparation method of aromatic diamine modified nano-attapulgite according to claim 1 is characterized in that organic solvent used in the preparation process is following any: acetone, and dimethyl formamide, processing dewaters before organic solvent uses.
3, the preparation method of aromatic diamine modified nano-attapulgite according to claim 1 is characterized in that used rare gas element is a nitrogen in the reaction process.
4, the preparation method of aromatic diamine modified nano-attapulgite according to claim 1, it is characterized in that using supercentrifuge that active intermediate product and aromatic diamine modified nano-attapulgite are carried out centrifugation, centrifuge speed is 4000-8000r/min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102443129A (en) * | 2011-10-24 | 2012-05-09 | 常州奥特纳新材料科技有限公司 | Method for preparing attapulgite/polyurethane composite material |
| CN102618108A (en) * | 2012-02-06 | 2012-08-01 | 常州大学 | Ultraviolet curing coating additive, preparation method and application thereof |
| CN102627873A (en) * | 2012-03-27 | 2012-08-08 | 南京信息工程大学 | Method for modifying attapulgite clay |
| CN105536723A (en) * | 2016-01-16 | 2016-05-04 | 常州大学 | Preparation method for beta-cyclodextrin grafted and modified attapulgite adsorption material |
| CN109705634A (en) * | 2019-01-15 | 2019-05-03 | 安徽大学 | A kind of concave convex rod soil matrix composite flame-retardant agent and its preparation and application with the modification of Nitrogen-and Phosphorus-containing organic matter |
| CN110041532A (en) * | 2019-05-21 | 2019-07-23 | 安徽大学 | A kind of novel attapulgite soil matrix composite flame-retardant agent and its preparation and application containing spirane structure |
| CN111471175A (en) * | 2020-04-26 | 2020-07-31 | 卢立文 | Wear-resistant nano SiO2-polyurea in-situ modified polyimide material and preparation method thereof |
| CN116693987A (en) * | 2023-08-08 | 2023-09-05 | 深圳市新中元电子有限公司 | Functional chip aluminum electrolytic capacitor and preparation method thereof |
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2007
- 2007-05-10 CN CNB2007100404876A patent/CN100475917C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443129A (en) * | 2011-10-24 | 2012-05-09 | 常州奥特纳新材料科技有限公司 | Method for preparing attapulgite/polyurethane composite material |
| CN102443129B (en) * | 2011-10-24 | 2013-09-25 | 常州奥特纳新材料科技有限公司 | Method for preparing attapulgite/polyurethane composite material |
| CN102618108A (en) * | 2012-02-06 | 2012-08-01 | 常州大学 | Ultraviolet curing coating additive, preparation method and application thereof |
| CN102618108B (en) * | 2012-02-06 | 2014-04-30 | 常州大学 | Ultraviolet curing coating additive, preparation method and application thereof |
| CN102627873A (en) * | 2012-03-27 | 2012-08-08 | 南京信息工程大学 | Method for modifying attapulgite clay |
| CN105536723A (en) * | 2016-01-16 | 2016-05-04 | 常州大学 | Preparation method for beta-cyclodextrin grafted and modified attapulgite adsorption material |
| CN109705634A (en) * | 2019-01-15 | 2019-05-03 | 安徽大学 | A kind of concave convex rod soil matrix composite flame-retardant agent and its preparation and application with the modification of Nitrogen-and Phosphorus-containing organic matter |
| CN110041532A (en) * | 2019-05-21 | 2019-07-23 | 安徽大学 | A kind of novel attapulgite soil matrix composite flame-retardant agent and its preparation and application containing spirane structure |
| CN110041532B (en) * | 2019-05-21 | 2021-08-31 | 安徽大学 | Attapulgite-based composite flame retardant containing spiro structure and preparation and application thereof |
| CN111471175A (en) * | 2020-04-26 | 2020-07-31 | 卢立文 | Wear-resistant nano SiO2-polyurea in-situ modified polyimide material and preparation method thereof |
| CN116693987A (en) * | 2023-08-08 | 2023-09-05 | 深圳市新中元电子有限公司 | Functional chip aluminum electrolytic capacitor and preparation method thereof |
| CN116693987B (en) * | 2023-08-08 | 2023-10-24 | 深圳市新中元电子有限公司 | Functional chip aluminum electrolytic capacitor and preparation method thereof |
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