CN100400607C - Preparation method of heat stability reinforced nano-montmorillonite - Google Patents
Preparation method of heat stability reinforced nano-montmorillonite Download PDFInfo
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- CN100400607C CN100400607C CNB2004100095830A CN200410009583A CN100400607C CN 100400607 C CN100400607 C CN 100400607C CN B2004100095830 A CNB2004100095830 A CN B2004100095830A CN 200410009583 A CN200410009583 A CN 200410009583A CN 100400607 C CN100400607 C CN 100400607C
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Abstract
The present invention relates to a method for organifying montmorillonite and a method for preparing nanometer organic montmorillonite with improved thermal stability, which belongs to the field of nanometer materials. The present invention is characterized in that imidazole class or pyridine class organic salts are used as organification modified agents in a nonaqueous solvent so as to realize organification reactions and good stripped dispersion of montmorillonite and obtain organic montmorillonite granules dispersed in nanometer dimensions, the solvent does not need to be separated, and the organic montmorillonite granules can be used directly; the solvent can also be further separated so as to obtain nanometer organic montmorillonite with good thermal stability. The organic montmorillonite prepared by the method has the advantages of good thermal resistance, high productivity and wide application ranges. The organic montmorillonite can be dispersed in various nonaqueous solvent media. Montmorillonite prepared by the method has good performance, so application ranges of nanometer organic montmorillonite are widened.
Description
Technical field
The invention belongs to field of nanometer material technology, be mainly concerned with the method for organ-mmt and strengthen the preparation method of the nano organic montmorillonite of thermostability.
Background technology
Polynite is a kind of 2: 1 type clay minerals of China's high yield, is a kind of layered silicate.About 1 nanometer of its lamellar spacing structurally long and widely is about 100 nanometers, is clipped between two silicon-oxy tetrahedrons by an alumina octahedral, forms laminate structure with shared Sauerstoffatom, and interlayer has tradable Na
+, Ca
2+, Mg
2+Deng positively charged ion, can and H
+, other metallic cation, the organic cation in the quaternary amine or other organic cation exchange.Wherein exchange, between cheating engaging layer, introduce alkyl chain and be the method for the most frequently used organ-mmt by the positively charged ion between alkyls quaternary amine and cheating engaging layer.This method that organises need consume a large amount of deionized waters when ion-exchange and washing, and because polynite forms colloid in water, suction filtration, difficulty is all compared in dry and pulverizing, reassociating of montmorillonite particle also is difficult to avoid in the drying process, the organic montmorillonoid interlamellar spacing prepared increases less, in polymkeric substance, peel off during following process and disperse difficult.Because alkyls quaternary amine heat decomposition temperature is lower, the organic montmorillonoid thermal stability of preparing is poor, when preparing the polymkeric substance montmorillonite composite material, when processing is used, cause degraded, the variable color of material owing to organic montmorillonoid thermal stability difference with this organic montmorillonoid.In addition, because the organic affinity of alkyls quaternary amine is poor, be unfavorable for that monomer or polymer diffusion enter between cheating engaging layer, polynite is difficult to peel off and is dispersed in the polymeric matrix.United States Patent 6,197,849 " Organophilic phyllosilicates "; Application number is 03129159.7 " a kind of preparation method of organo montmorillonite "; Application number is 01134604.3, " hydrophilic polynite and preparation method thereof "; Application number is 02153966.9, and " nano imvite and preparation method thereof " etc. all explored the method that organises of polynite and the preparation of nano imvite.Compare with other organic modifiers, imidazoles or pyridines organic salt have higher thermostability, lower saturation vapour pressure has stronger bonding force after the ion-exchange and between montmorillonite layer, help improving the consistency of polynite and material and the thermostability of matrix material.Utilize organic solvent dissolution imidazoles or pyridines organic salt, again polynite is dispersed in the solution, realize organising of polynite, do not appear in the newspapers thereby make organo montmorillonite in solution, reach the be enhanced preparation method of nano imvite of thermostability of nano-dispersed.
Summary of the invention
One of purpose of the present invention provides the treatment process that organises of polynite.
Two of purpose of the present invention provides the preparation method of the nano imvite that strengthens thermostability.
Three of purpose of the present invention is to utilize imidazoles or pyridines organic salt as the organic modification agent, a kind of organising of polynite of realizing in non-aqueous solvent is provided, obtain the limellar stripping of polynite and the method for nano-dispersed, thus the nano imvite of the thermostability that is enhanced.
Four of purpose of the present invention is that will to prepare thermal stability good, can be dispersed in the nano organic montmorillonite in the multiple polymers system.
The preparation method of the nano imvite of enhancing thermostability of the present invention may further comprise the steps:
(1) imidazoles or pyridines organic salt are dissolved in and form solution in the organic solvent
Imidazoles or pyridines organic salt are dissolved in the organic solvent, heating, stirring, controlled temperature is at 20 ℃～60 ℃, and the weight ratio of imidazoles or pyridines organic salt and organic solvent is 1/40～1/10;
(2) preparation of organ-mmt and nano organic montmorillonite
Polynite is joined in the solution of step (1) and keep 20 ℃～60 ℃ of temperature of reaction, stirred 5～24 hours, make the positively charged ion between imidazoles or pyridines organic salt molecule and cheating engaging layer fully exchange and enter between cheating engaging layer, finish the reaction that organises of polynite, wherein, the weight ratio of imidazoles or pyridines organic salt and polynite is 1/10～1/2; Polynite with laminated structure peel off become to organise, monolithic dispersive nano imvite particle, obtain containing the colloidal solution of nano organic montmorillonite particle, the colloidal solution that contains this nano organic montmorillonite particle can directly use; Also can further separate the dry and nano organic montmorillonite of the thermostability that is enhanced.
Method of the present invention is as the organic modification agent with imidazoles or pyridines organic salt, non-aqueous solvent with this type of organic salt of solubilized is a medium, 20 ℃～60 ℃ stirrings, makes the dissolving of imidazoles or pyridines organic salt, add polynite again, continue to stir 5～24 hours.Because positively charged ion and the positively charged ion between cheating engaging layer in the organic salt molecule have very strong exchange capacity, by ion-exchange, the organic salt molecule has entered between cheating engaging layer, realized that the organising of polynite, montmorillonite layer spacing increase and limellar stripping disperses, obtained the organo montmorillonite size of particles in nanometer range.Because the good solubility of organic salt molecule in solvent, along with the organic salt molecule enters between cheating engaging layer, solvent molecule also enters between cheating engaging layer, further weakened the interaction between the montmorillonite layer, under the heating and the effect of stirring, peeled off the montmorillonite layer that is dispersed into nano organic and be dispersed in the medium.Molecular structure by changing imidazoles or pyridines organic salt and anion species just can obtain being dissolved in the organic salt of different non-aqueous solvents, realize polynite in different media organise and nanometer is peeled off dispersion.The nano organic montmorillonite that is dispersed in the different non-aqueous solvent media can satisfy multiple application demand, as coatings industry, is with a wide range of applications.
By suction filtration, washing and vacuum-drying can be separated the nano organic montmorillonite that is dispersed in the organic solvent.Imidazoles or pyridines organic salt with different molecular structures organise to polynite, and the nano organic montmorillonite that obtains can be dispersed in the different polymeric matrixs, and have good avidity with polymeric matrix.
The present invention utilizes the imidazoles of good heat resistance or pyridines organic salt as the organic modification agent in non-aqueous solvent, realized polynite organise and montmorillonite layer peel off dispersion, wherein the weight ratio of organic salt and solvent is 1/40～1/10, and the weight ratio of organic salt and polynite is 1/10～1/2.Preparation process is done solvent phase with water and is lacked than having solvent load, and the solvent in the system can be used as the solvent of next step reaction or processing or the characteristics that medium uses, and can simplify technology, saves cost.As not needing solvent to use as the medium of subsequent reactions, the solvent behind the suction filtration can be used further to the preparation of nano organic montmorillonite.
Described polynite is Na-polynite, Ca-polynite, Mg-polynite, Li-polynite, H-polynite, natural montmorillonite, synthetic polynite or their any mixture; The cation exchange capacity of polynite is 80～120meq/100g.
Described imidazoles or pyridines organic salt are the mixtures with one or more salt of following structure.R in the formula, R
1, R
2Being saturated or unsaturated alkyl, can be straight-chain alkyl, also can be the alkyl with side chain, and the carbonatoms of alkyl is between 1～20.X
-Be selected from halide anions such as (1) chlorine, bromine or iodine; (2) negatively charged ion such as acetate, sulfate radical or tetrafluoroborate.Further contain other substituting groups such as hydroxyl, amino in the described alkyl.
The general structure of the general structure pyridines organic salt of imidazoles organic salt
Used organic solvent is organic solvent or their any mixture such as dimethylbenzene, toluene, dehydrated alcohol, anhydrous methanol, chloroform, acetone, ethylene dichloride, but be not limited to these organic solvents, as long as can make the dissolving of corresponding organic salt under room temperature or heating (60 ℃), and the needs that satisfy next step preparation feedback get final product.
Separation of the present invention be will contain the nano organic montmorillonite particle colloidal solution in the time of 20 ℃～60 ℃, suction filtration while hot while stirring.After respectively washing about 3 times with small amount of deionized water and ethanol, filter cake is placed in 60～80 ℃ of vacuum drying ovens, and dry about 24～48 hours, the nano organic montmorillonite of the thermostability that is enhanced.
The preparation that strengthens the nano organic montmorillonite of thermostability is to carry out in non-aqueous solvent, has avoided the generation of polynite cohesion, and the productive rate height is more easily carried out in the reaction that organises.Between the dried organic montmorillonoid particle a little less than the bonding force, help pulverizing and process the dispersion when using.
The load of preparation, medicine and the catalyzer that nano organic montmorillonite colloidal solution among the present invention can be directly used in coating, polymkeric substance Nano composite material of montmorillonite on montmorillonite layer, preparation of makeup etc.Method preparation technology of the present invention is simple, and solvent utilization ratio height does not have or rarer solvent slop produces, and helps environment protection.
The organic salt resistance toheat of using among the present invention is good, and chemical property is stable, and the polynite resistance toheat that organises through such salt is good, compares with common alkyls quaternary amine, and heat decomposition temperature can improve 50～200 ℃.
The organo montmorillonite resistance toheat that the present invention prepares is good, and the productive rate height can be dispersed in the multiple non-aqueous solvent medium, has wide range of applications.Because the polynite that the inventive method is prepared has superperformance, widened the field that nano organic montmorillonite is used.
Description of drawings
The electron scanning micrograph of Fig. 1 a. embodiment of the invention 1.
The electron scanning micrograph of Fig. 1 b. Comparative Examples.
Fig. 2. the thermogravimetric curve figure of the nano imvite of the enhancing thermostability of the embodiment of the invention 2 and Comparative Examples.
Embodiment
Just the present invention will be described for following specific examples, but these examples only are partial contents of the present invention, and the present invention is not limited to these contents.
Embodiment 1
Get 100 milliliters of dimethylbenzene, 0.25 gram 1-methyl-3-tetradecyl imidazolium chloride salt, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 40 ℃ of controlled temperature, stir the Na-polynite that added 0.5 gram in 5 hours to the transparent clarification of solution again, continue to stir 24 hours, obtain the colloidal solution of organo montmorillonite.Get solution rotating and film on the sheet mica of cleaning, use sem observation after the vacuum-drying, the discovery polynite has been peeled off and has been dispersed into nanoparticle, as shown in Figure 1a.
Comparative Examples 1
Get the Na-polynite of 100 milliliters of dimethylbenzene and 0.5 gram, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 40 ℃ of controlled temperature continue to stir 24 hours, obtain the suspension of polynite.Get the suspension spin-coating on the sheet mica of cleaning, use sem observation after the vacuum-drying, find the unstripped nano particle that is dispersed into of polynite, still be the micron order macrobead of reunion shape, shown in Fig. 1 b.
Embodiment 2
Get 200 milliliters of dimethylbenzene, 0.5 gram 1-methyl-3-hexadecyl bromination imidazole salts, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 40 ℃ of controlled temperature, stir the Ca-polynite polynite that added 1 gram in 5 hours to the transparent clarification of solution back, continue to stir 24 hours, obtain the colloidal solution of organo montmorillonite.With No. three sand core funnels suction filtration while hot, filter cake is drained after respectively washing three times with deionized water and ethanol, take out filter cake 60 ℃ of vacuum-dryings 24 hours, obtain organic montmorillonoid (O-MMT1), the thermal weight loss test shows, organic montmorillonoid (O-MMT1) is compared with the organic montmorillonoid of handling with cetyl trimethylammonium bromide, and resistance toheat is significantly improved, as shown in Figure 2.
Comparative Examples 2
Get 200 milliliters of dimethylbenzene, 0.5 gram cetyl trimethylammonium bromide, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 40 ℃ of controlled temperature, stir the Ca-polynite that added 1 gram in 5 hours to the transparent clarification of solution back, continue to stir 24 hours, obtain the colloidal solution of organo montmorillonite.With No. three sand core funnels suction filtration while hot, filter cake is drained after respectively washing three times with deionized water and ethanol, take out filter cake 60 ℃ of vacuum-dryings 24 hours, obtain organic montmorillonoid (O-MMT2), the thermal weight loss test shows, this organic montmorillonoid (O-MMT2) is compared with the organic montmorillonoid that 1-methyl-3-hexadecyl bromination imidazole salts is handled, and thermal stability is obviously relatively poor, as shown in Figure 2.
Embodiment 3
Get 100 milliliters of toluene, 0.35 gram 1-vinyl-3-hexadecyl iodate imidazole salts, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 40～50 ℃ of controlled temperature, stir and to the transparent clarification of solution, added the 1 Mg-polynite polynite that restrains again in 8 hours, continue to stir 24 hours, obtain being dispersed in nanoscale the suspension of the organo montmorillonite in the toluene, isolated organo montmorillonite, its weight loss of dry back are that 5% o'clock heat decomposition temperature is 370 ℃ (nitrogen atmosphere), use cetyl trimethylammonium bromide, by handle resulting organo montmorillonite with quadrat method, weight loss is 5% o'clock 251 ℃ of heat decomposition temperatures (nitrogen atmosphere), and 1-vinyl-3-hexadecyl iodate imidazole salts is handled resulting organo montmorillonite heat decomposition temperature and improved 100～120 ℃.
Embodiment 4
Get 100 milliliters of dehydrated alcohols, 0.272 gram 4-methyl-N-fluorobutane borate pyridinium salt, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 30～40 ℃ of controlled temperature, stir the Li-polynite that added 1 gram in 5 hours to the transparent clarification of solution again, continue to stir 24 hours, obtain the suspension of organo montmorillonite, scanning electron microscope result shows that polynite is dispersed in the ethanol with nanoscale, after the isolated organo montmorillonite drying, its heat decomposition temperature is compared by handle resulting organo montmorillonite with quadrat method with cetyl trimethylammonium bromide, and heat decomposition temperature improves 70～100 ℃.
Embodiment 5
Get 100 milliliters of chloroforms, 0.25 gram 1-methyl-3-butylacetic acid imidazole salts, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 30～40 ℃ of controlled temperature, stir the H-polynite that added 1 gram in 2 hours to the transparent clarification of solution again, continue to stir 12 hours, obtain the suspension of organo montmorillonite.Isolated organo montmorillonite respectively washs three times with deionized water and ethanol, and after the drying, its heat decomposition temperature is compared by handle resulting organo montmorillonite with quadrat method with cetyl trimethylammonium bromide, and heat decomposition temperature improves 60～80 ℃.
Embodiment 6
Get 100 milliliters of ethylene dichloride, 0.5 restrain 1,2-dimethyl-3-(the amino hexadecyl of 6-) sulfuric acid imidazole salts adds in the single port flask, puts into magnetic stir bar, reflux condensing tube is installed, oil bath heating, 50～60 ℃ of controlled temperature stir and added 1 natural montmorillonite that restrains again in 2 hours to the transparent clarification of solution, continue to stir 12 hours, obtain the suspension of organo montmorillonite.Isolated organo montmorillonite respectively washs three times with deionized water and ethanol, and after the drying, its heat decomposition temperature and usefulness dimethyl ceryl brometo de amonio are compared 50～70 ℃ of heat decomposition temperature raisings by handle resulting organo montmorillonite with quadrat method.
Embodiment 7
Get 100 milliliters of acetone, 0.2 gram 1-methyl-3-allyl group Tetrafluoroboric acid imidazole salts, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the synthetic polynite that adds 1 gram after stirring at room 0.5 hour mixes to solution again continues to stir 6 hours, obtains the suspension of organo montmorillonite.Isolated organo montmorillonite respectively washs three times with deionized water and ethanol, after the drying, its heat decomposition temperature with handle (treatment process is identical) resulting organo montmorillonite with cetyl trimethylammonium bromide and compare, heat decomposition temperature improves 100～120 ℃.
Get the mixture (volume ratio is 1/1) of 100 milliliters of toluene and dimethylbenzene, 0.3 gram 1-methyl-3-(4-hydroxyl decyl) phosphorus hexafluoride imidazole salts, add in the single port flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 50～60 ℃ of controlled temperature, stir and to the transparent clarification of solution, added 1 mixing polynite (the Na-polynite that restrains again in 1 hour, H-polynite and Li-polynite 40/30/30 mix by weight percentage), continue to stir 12 hours, obtain the suspension of organo montmorillonite.Isolated organo montmorillonite respectively washs three times with deionized water and ethanol, and after the drying, its heat decomposition temperature and usefulness trimethylammonium hexadecyl brometo de amonio are compared 60～80 ℃ of heat decomposition temperature raisings by handle resulting organo montmorillonite with quadrat method.
Claims (6)
1. preparation method who strengthens the nano imvite of thermostability, it is characterized in that: described method may further comprise the steps:
(1) imidazoles or pyridines organic salt are dissolved in and form solution in the organic solvent
Imidazoles or pyridines organic salt are dissolved in the organic solvent, heating, stirring, controlled temperature is at 20 ℃～60 ℃;
(2) preparation of organ-mmt and nano organic montmorillonite
Polynite is joined in the solution of step (1) and keep 20 ℃～60 ℃ of temperature of reaction, stir, make the positively charged ion between imidazoles or pyridines organic salt molecule and cheating engaging layer fully exchange and enter between cheating engaging layer, finish the reaction that organises of polynite, wherein, the weight ratio of imidazoles or pyridines organic salt and polynite is 1/10～1/2; Polynite with laminated structure peel off become to organise, monolithic dispersive nano imvite particle, obtain containing the colloidal solution of nano organic montmorillonite particle, separate drying, the nano organic montmorillonite of the thermostability that is enhanced;
Described imidazoles or pyridines organic salt are the mixtures with one or more salt of following structure;
Structure with the structure pyridines organic salt of imidazoles organic salt
R wherein, R
1, R
2Being saturated or unsaturated alkyl, is straight-chain alkyl or the alkyl with side chain, and the carbonatoms of alkyl is between 1～20;
X
-Be selected from (1) chlorine, bromine or iodine halide anion; (2) acetate, sulfate radical or tetrafluoroborate negatively charged ion.
2. method according to claim 1 is characterized in that: described polynite is Na-polynite, Ca-polynite, Mg-polynite, Li-polynite, H-polynite, natural montmorillonite, the synthetic polynite of inorganic salt or their any mixture; The cation exchange capacity of polynite is 80～120meq/100g.
3. method according to claim 1 is characterized in that: the weight ratio of described step (1) imidazoles or pyridines organic salt and organic solvent is 1/40～1/10.
4. method according to claim 1 is characterized in that: further contain hydroxyl or amino substituting group in the described alkyl.
5. according to claim 1 or 3 described methods, it is characterized in that: described organic solvent is dimethylbenzene, toluene, dehydrated alcohol, anhydrous methanol, chloroform, acetone, ethylene dichloride or their any mixture.
6. method according to claim 1, it is characterized in that: described separation is the colloidal solution that will contain the nano organic montmorillonite particle at 20 ℃～60 ℃ suction filtrations while stirring, filter cake deionized water and washing with alcohol, then in 60～80 ℃ of vacuum drying ovens, drying, the nano organic montmorillonite of the thermostability that is enhanced.
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