CN100347201C - Method of preparing polymer/montmorillonid nano-composite material by montmorillonoid in-situ organization - Google Patents
Method of preparing polymer/montmorillonid nano-composite material by montmorillonoid in-situ organization Download PDFInfo
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Abstract
The present invention particularly relates to a method for preparing a polymer / montmorillonite nanometer composite material by organifying montmorillonite in situ, which belongs to the field of polymer nanometer materials. Imidazole class or pyridine class organic salts are used as organic modifying agents in a nonaqueous solvent so as to realize the organification and the stripped dispersion of the montmorillonite and form a colloid solution that the particle size of the organic montmorillonite is in a nanometer range. Solvents with different performance and organic salts with different molecular structures can be used for meeting requirements for preparing polymer / montmorillonite nanometer materials with different performance. Compared with other organic modified agents, the imidazole class or the pyridine class organic salts have the advantages of high thermal stability, low saturated vapor pressure and strong adhesion with slice layers of the montmorillonite after ion exchange, and the method is favorable to enhancing compatibility between the montmorillonite and polymeric materials and thermal stability of composite materials.
Description
Technical field
The invention belongs to the polymer nano material field, specially refer to montmorillonoid in-situ and organise and prepare the method for nano composite polymer-montmorillonoid material.
Background technology
Polynite is bentonitic main component, is the clay mineral of a kind of high yield of China, has obtained in fields such as chemical industry, medicine, oil, casting, materials to use widely.Macromolecular material is a type material with the fastest developing speed, and it is used and has spread all over people's production and various fields in life.The a large amount of clay mineral materials that exist of macromolecular material and nature are combined, and it is more good to produce performance, and range of application is wider, and the advanced composite material that price is more cheap is people's a wonderful dream.Along with the development of nanotechnology, the polynite that people wish to have nano-lamellar structure is peeled off and is dispersed in the polymkeric substance Nano composite material of montmorillonite that obtains excellent property in the polymeric matrix or have property.One of key of preparation polymkeric substance Nano composite material of montmorillonite is organising of montmorillonite layer, improves consistency between montmorillonite layer and the polymeric matrix with expectation; Two of key is fully peeling off and being dispersed in the polymeric matrix of montmorillonite layer, demonstrates the premium properties of nano composite material.Existing organ-mmt process is to realize in the aqueous solution.Granted publication number is CN1125125C " level polypropylene/montmorillonoid intercalation material preparation method "; Publication number is CN1267682A " a kind of composite nanometer-level polypropylene/montmorillonoid material and preparation method "; Publication number is CN1375515A " a kind of nano composite polymer-montmorillonoid material and a method for making thereof "; Publication number is CN1344759A " composite nano polypropylene mixture/montmorillonoid nano-material and preparation method thereof "; Publication number is CN1459460A " a kind of polyolefin/montmorillonite nano composite material and a method for making "; Notification number is CN1055706C " a kind of nanometer composite polyamide-clay material and preparation method thereof "; Notification number is CN1081207C " a kind of method for making of polymeric amide clay nanocomposites "; Application number is that 01109844.9 relevant patents such as " a kind of nanometer montmorillonoid-containing composite materials and preparation method thereof " and all pertinent literatures of having delivered all adopt this method, and water is to use as the solvent or the dispersion medium of preparation polymkeric substance Nano composite material of montmorillonite under most of situation, the organic montmorillonoid that is dispersed in the water need be through filtration, washing, dry and pulverizing, need to consume a large amount of deionized water, preparation process and complex process.And, in the organic montmorillonoid preparation process, the dispersive montmorillonite layer reassociate and the gelation of montmorillonite particle is difficult to avoid, this will directly have influence on the preparation polymkeric substance and cover and take off the peeling off and disperse in polymeric matrix of polynite in the nano composite material process." Thermal DegradationChemistry of Alkyl Quaternary Ammonium Montmorillonite " (Chem.Mater.2001,13,2979-2990) etc. literature research shows, the heat decomposition temperature of existing organ-mmt properties-correcting agent is lower, in the processing of matrix material and use, decompose, cause the degraded and the variable color of polymkeric substance.
Summary of the invention
One of purpose of the present invention is to prepare that to have resistance toheat good, the nano composite polymer-montmorillonoid material that anti-degradation capability is strong.
Two of purpose of the present invention is to utilize imidazoles or pyridines organic salt as the organic modification agent, provide a kind of in non-aqueous solvent the organising of in-situ accomplishes polynite, preparation method that montmorillonite layer is peeled off the dispersive nano composite polymer-montmorillonoid material.
The present invention is fully taking into account on the basis of prior art, select the imidazoles or the pyridines organic salt of different solvents and different molecular structures for use according to different polymeric systems, with polynite organise and the preparation of polymer composites combines together, avoided removing reassociating and gelation of polynite in solvent and the preparation organic montmorillonoid process, guaranteed fully peeling off and the nano-dispersed in matrix of montmorillonite layer, simplified separated from solvent in the organic montmorillonoid preparation process, vacuum-drying, pulverizing and with the redispersion process of polymkeric substance compound tense.Because imidazoles or pyridines organic salt have higher thermotolerance and lower volatility, in the processing of matrix material and use, can not cause the degraded and the variable color of polymkeric substance owing to the decomposition of organic modification agent, can not cause owing to the volatilization of organic modifiers yet polynite go organise and the small molecules volatile matter to the pollution of environment.
The present invention is applicable to the polynite/polar polymer of preparation nano-dispersed, polynite/non-polar polymer, polynite/thermoplastic polymer, fields such as polynite/thermoset polymer composite.
Method of the present invention can be divided into according to the preparation process and the requirement of differing materials:
Stir and the condition of control certain temperature under, polymkeric substance is added in the slurry of nano organic montmorillonite and carries out solution blending.
2. the slurry that contains nano organic montmorillonite is after removing most of solvent, and hygrometric state condition descends and polymkeric substance carries out melt blending.
3. stirring and controlling under the condition of certain temperature, addition polymerization or the addition copolymerization of polymer monomer in the slurry of nano organic montmorillonite.
4. stirring and controlling under the condition of certain temperature, polymer monomer carries out coordination and ionic polymerization in the slurry of nano organic montmorillonite.
5. stirring and controlling under the condition of certain temperature, polymer monomer carries out condensation polymerization in the slurry of nano organic montmorillonite.
6. stirring and controlling under the condition of certain temperature, polymer monomer carries out polyaddition in the slurry of nano organic montmorillonite, as the preparation of urethane Nano composite material of montmorillonite.
7. stirring and controlling under the condition of certain temperature, performed polymer carries out open loop, chain extension and crosslinking reaction in the slurry of nano organic montmorillonite.
The montmorillonoid in-situ of the present invention method for preparing nano composite polymer-montmorillonoid material that organises may further comprise the steps:
(1) in non-aqueous solvent with imidazoles or pyridines organic salt as organic modifiers, under the effect of stirring, controlled temperature is 20 ℃～60 ℃, make imidazoles or pyridines organic salt be dissolved to transparent clarification in solvent, the weight ratio of general imidazoles or pyridines organic salt and organic solvent is 1/40～1/10; Add polynite again, the mol ratio of imidazoles or pyridines organic salt and polynite is 2: 1, keeps temperature of reaction, stirs 5～24 hours, realized that the organising of polynite, montmorillonite layer spacing increase and limellar stripping disperses, obtained the organo montmorillonite size of particles in nanometer range.
(2) step (1) is contained the slurry of nano organic montmorillonite particle and thermoplastic resin or rubber and carries out the in-situ solution blend, melt extrudes blend, or with the thermosetting resin crosslinking curing, obtain polynite/polymer nanocomposites;
Or
(1) imidazoles or pyridines organic salt are dissolved in the polymerization single polymerization monomer as properties-correcting agent, stir, controlled temperature is 20 ℃～60 ℃, add polynite again, wherein the mol ratio of imidazoles or pyridines organic salt and polynite is 2: 1, stirs, obtain the slurry of organo montmorillonite size of particles in nanometer range (at different polymerization single polymerization monomers, for ease of carrying out step (2), catalyzer can be added, in slurry) as cobaltous acetate, antimonous oxide etc.;
(2) slurry that step (1) is contained the nano organic montmorillonite particle is carried out the body of the body of solution polymerization, vinyl monomer of olefinic monomer or solution polymerization, functional monomer or solution condensation polymerization, the monomeric poly-addition polymerization of synthesis of polyurethane obtains nano composite polymer-montmorillonoid material.
With step (1) contain the body of the slurry of nano organic montmorillonite particle and olefinic monomer solution polymerization, vinyl monomer polymerization, functional monomer or solution condensation polymerization, the monomeric poly-addition polymerization of synthesis of polyurethane obtains nano composite polymer-montmorillonoid material.
The polynite in the described slurry that contains the nano organic montmorillonite particle and the mass percent of thermoplastic resin, rubber or thermosetting resin are 5～10: 95～90.
Polynite and the monomeric mass percent of olefinic monomer, vinyl monomer, functional monomer or synthesis of polyurethane in the described slurry that contains the nano organic montmorillonite particle are 5～10: 95～90.
The nano composite polymer-montmorillonoid material that the present invention prepares can be used as coating, and tackiness agent or slurry use, and the solvent in original system can be used as the dispersion medium of preparation process and product; If when using as solid materials such as plastics, rubber and fibers, the solvent in the system can be recycled.
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.
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, benzene, dehydrated alcohol, anhydrous methanol, acetone, chloroform, tetracol phenixin, ethylene dichloride, Ethylene Dichloride, methyl-sulphoxide, but be not limited to these organic solvents, as long as can make corresponding organic salt dissolving under room temperature or heating (60 ℃), the organic solvent that can be used as polymkeric substance/nano montmorillonite composite material preparation uses.
Described thermoplastic resin is polyvinyl chloride, polyvinyl acetate (PVA), polyethylene, polypropylene, polystyrene, nitrile benzene resin, nitrile butadiene styrene resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, nylon-6, polymethylmethacrylate, ethylene-propylene copolymer, butadiene-styrene block copolymer or silicone resin etc.
Described rubber is urethane, cis-1,4-polybutadiene rubber, chloroprene rubber, paracril, styrene-butadiene rubber(SBR), acrylic elastomer or chlorinated rubber etc.
Described thermosetting resin is urea aldehyde, phenolic aldehyde, epoxy or polyimide resin etc.
Described olefinic monomer is ethene, propylene, isoprene or divinyl.
Described vinyl monomer is vinylchlorid, vinylbenzene, methyl methacrylate, vinyl acetate or vinyl cyanide.
Described functional monomer is hexanolactam, epoxy chloropropane, dihydroxyphenyl propane, terephthalic acid, ethylene glycol, butyleneglycol, vulcabond, polyether glycol or polyester polyol.
The present invention be in non-aqueous solvent with imidazoles or pyridines organic salt as properties-correcting agent, realize organising, peel off and nano-dispersed of polynite.The nano organic montmorillonite particle that is dispersed in the non-aqueous solvent can directly use, and in-situ preparing goes out nano composite polymer-montmorillonoid material.
Because the solvent in the colloidal solution can be used as the medium of further preparation matrix material, but the nano organic montmorillonite particle original position that is dispersed in the solvent directly use, need not to separate.Organic modifiers of the present invention is compared the school with other organic modifiers, imidazoles or pyridines organic salt have higher thermostability, lower saturation vapour pressure, and stronger bonding force is arranged after the ion-exchange and between montmorillonite layer, help improving the consistency between polynite and the polymer materials and the thermostability of matrix material.
Characteristics of the present invention are:
1. in non-aqueous solvent, carry out organising and disperseing of polynite, peeling off of the organising of polynite, montmorillonite layer disperseed and the preparation of nano composite polymer-montmorillonoid material combines together, avoided the gelation in the organic montmorillonoid preparation process and reassociated, guaranteed that polynite is dispersed in the polymeric matrix with nano-scale, simplified preparation process, reduced preparation cost, it is cheap to have opened up preparation, the new way of the nano composite polymer-montmorillonoid material of excellent property.
2. imidazoles that structure is different or pyridines organic salt can dissolve in different solvents, so can in different solvents, finish the preparation of the organising of polynite, nano-dispersed and nano composite polymer-montmorillonoid material, the preparation method is simple, and the scope of application is wide.
3. imidazoles or pyridines organic salt good heat resistance, volatility is low, can prevent in materials processing and use polynite go organise, the small molecules volatile matter is to the pollution of environment and the degraded and the variable color of matrix material.
Description of drawings
The XRD curve of 1Na-polynite of Fig. 1 a. embodiment of the invention and Na-polynite/miaow Cuo salt/nanometer composite polypropylene material.
The section electromicroscopic photograph of Fig. 1 b. embodiment of the invention 1Na-polynite/miaow Cuo salt/nanometer composite polypropylene material.
The XRD curve of Fig. 2 a. Comparative Examples 1Na-polynite/nanometer composite polypropylene material.
The thermogravimetric curve of Fig. 2 b. Comparative Examples 1Na-polynite/nanometer composite polypropylene material and Na-polynite/miaow Cuo salt/nanometer composite polypropylene material.
Fig. 3. the thermogravimetric curve figure of Comparative Examples 2Na-polynite/quaternary amine/nanometer composite polypropylene material and Na-polynite/miaow Cuo salt/nanometer composite polypropylene material.
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 250 milliliters of there-necked flasks, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 40 ℃ of controlled temperature stir 5 hours to the transparent clarification of solution, add the Na-polynite of 0.5 gram again, continue to stir 24 hours, obtain the slurry of organo montmorillonite.Then, add 9.5 gram isotatic polypropylene, be warming up to 140 ± 2 ℃, stirred 24 hours.While hot the polymers soln in the flask is poured in a large amount of ethanol, the floss that is settled out is filtered and respectively washs three times with deionized water and ethanol, vacuum-drying, obtain the level polypropylene/montmorillonoid matrix material, XRD and TEM characterization result show that this matrix material is a composite nanometer-level polypropylene/montmorillonoid material, sees accompanying drawing 1a and 1b.
Comparative Examples 1
Get 100 milliliters of dimethylbenzene, add in 250 milliliters of there-necked flasks, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, controlled temperature adds the Na-polynite of 0.5 gram at 40 ℃, stirs 24 hours, obtains the slurry of polynite.The isotatic polypropylene that in slurry, adds 9.5 grams, be warming up to 140 ± 2 ℃, stirred 24 hours, while hot the mixture in the flask is poured in a large amount of ethanol, the floss that is settled out is filtered and respectively washs three times with deionized water and ethanol, and vacuum-drying obtains the polypropylene montmorillonite composite material, the XRD characterization result shows in this matrix material that montmorillonite layer do not peel off and reach nano-dispersed, sees accompanying drawing 2a; TGA test shows, the resistance toheat of material do not have the composite nanometer-level polypropylene/montmorillonoid material of preparation in the example 1 good, see accompanying drawing 2b.
Comparative Examples 2
Get 100 milliliters of dimethylbenzene, 0.25 gram hexadecyl brometo de amonio (quaternary ammonium salt), add in 250 milliliters the there-necked 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 back, continue to stir 24 hours, obtain the slurry of organo montmorillonite, then, add the isotatic polypropylene of 9.5 grams, be warming up to 140 ± 2 ℃, stirred 24 hours, while hot the polymers soln in the flask is poured in a large amount of ethanol, after the floss that is settled out filtered and respectively washing three times with deionized water and ethanol, vacuum-drying obtains the polypropylene Nano composite material of montmorillonite, the TGA test shows, the initial decomposition temperature of material is lower than the composite nanometer-level polypropylene/montmorillonoid material of preparation among the embodiment 1, shows relatively poor thermostability, sees accompanying drawing 3.
Embodiment 2
0.25 the 1-methyl-3-hexadecyl Tetrafluoroboric acid imidazole salts of gram is under the 80 ℃ of vacuum-drying 6 hours, 100 ℃ of synthetic polynites of 0.5 gram; after the vacuum-drying 6 hours; add in the there-necked flask of 250 milliliters of exsiccant, add again and put into the exsiccant magnetic stir bar, add 100 milliliters of dry toluene that refluxed with syringe; reflux condensing tube is installed; under nitrogen protection, heating in water bath, 50 ± 2 ℃ of controlled temperature; stirred 24 hours, and obtained the slurry of organo montmorillonite.Other gets two mouthfuls of flasks of 250 milliliters of cleanings, exsiccant, put into the exsiccant magnetic stir bar, seal bottleneck with anti-mouthful of soft rubber ball, behind the pump drainage three times, the colloidal solution that extracts 50 milliliters of organo montmorillonites injects flask, feeding propylene gas to pressure is 770mmHg, adds 3 milliliters of MAO (1.4mol/l), 2 milliliters Me
2Si (Ind)
2ZrCl
2(1.5 μ m/l), 40 ℃ of following polymerizations add acidifying ethanol termination reaction after about 30 minutes, and with deionized water and washing with alcohol polymerisate, vacuum-drying obtains composite nanometer-level polypropylene/montmorillonoid material.
Embodiment 3
0.35 1-methyl-3-(4-ethyl-hexadecyl) Tetrafluoroboric acid imidazole salts of gram; 80 ℃ of vacuum-drying 6 hours; 0.5 under 100 ℃ of the gram mixing polynites (mass percent of Na-polynite and Ca-polynite is 80/20); after the vacuum-drying 6 hours; add in the there-necked flask of 250 milliliters of exsiccant; add again and put into the exsiccant magnetic stir bar; add 100 milliliters of dry toluene that refluxed with syringe; reflux condensing tube is installed; under nitrogen protection, heating in water bath, 50 ± 2 ℃ of controlled temperature; stirred 24 hours, and obtained the slurry of organo montmorillonite.Other gets two mouthfuls of flasks of 250 milliliters of cleanings, exsiccant, puts into the exsiccant magnetic stir bar, seals bottleneck with an anti-mouthful soft rubber ball, behind the pump drainage three times, extract the slurry of 50 milliliters of organo montmorillonites and inject flask, feeding ethylene gas to pressure is 770mmHg, adds the AlEt of 2 mmoles
3, the MAO of 3 mmoles (1.4mol/l), 2 milliliters Et (Ind)
2ZrCl
2(1.5 μ m/l) after about 30 minutes, adds acidifying ethanol termination reaction 30 ℃ of following polymerizations, and with deionized water and washing with alcohol polymerisate, vacuum-drying obtains polyethylene/montmorillonite nanometer composite material.
Embodiment 4
Get the 1-methyl-3-octadecyl iodate imidazole salts of 0.25 gram, 0.5 gram Li-polynite, add in 250 milliliters the single port flask, put into magnetic stir bar, add 100 milliliters of dimethylbenzene, reflux condensing tube is installed, heating in water bath, controlled temperature stirred 24 hours at 50 ± 2 ℃, obtained the slurry of organo montmorillonite.Weight ratio by polypropylene and Li-polynite is 95/5, and the slurry that adds organo montmorillonite is carried out melt blending, in processing and last handling process drying, remove solvent and obtain composite nanometer-level polypropylene/montmorillonoid material.
Get 100 milliliters of N,N-DIMETHYLACETAMIDEs, 0.25 gram 1-methyl-3-butylacetic acid imidazole salts, add in 250 milliliters the there-necked flask, put into magnetic stir bar, reflux condensing tube is installed, the oil bath heating, 60～80 ℃ of controlled temperature, stir the H-polynite that added 1 gram in 1 hour to the transparent clarification of solution again, continue to stir 12 hours, obtain the slurry of organo montmorillonite, add 0.6 mole 4,4-diamino-phenyl ether and 0.3 mole of pyromellitic acid dianhydride are warming up to 150～200 ℃ of reactions 2 hours, obtain the polyimide Nano composite material of montmorillonite after removing solvent.
Embodiment 6
Get 100 milliliters of vinylbenzene; 1 gram 1-methyl-3-allyl group Tetrafluoroboric acid imidazole salts; 4 gram Ca-polynites; add in 250 milliliters the there-necked flask; install mechanical stirring, reflux condensing tube, stirring at room obtained the vinylbenzene slurry of polynite in 12 hours; behind the ultra-sonic dispersion 1 hour; add 1,1-di-n-butyl peroxidation hexahydroaniline 0.05 gram stirred 1 hour; logical argon shield; oil bath is heated to 100 ℃, and the limit heating is till the limit is stirred to and is fixed up; reacted 16 hours, and obtained the polystyrene Nano composite material of montmorillonite.
Embodiment 7
Get 100 milliliters of methyl methacrylates; 1 gram 1-methyl-3-(4-hydroxyl decyl) phosphorus hexafluoride imidazole salts; 4 gram Mg-polynites; add in 250 milliliters the there-necked flask; install mechanical stirring, reflux condensing tube, stirring at room obtained the methyl methacrylate slurry of polynite in 12 hours; behind the ultra-sonic dispersion 1 hour; add 1,1-di-n-butyl peroxidation hexahydroaniline 0.05 gram stirred 1 hour; logical argon shield; oil bath is heated to 80 ℃, and the limit heating is till the limit is stirred to and is fixed up; reacted 5 hours, and obtained the polymethylmethacrylate Nano composite material of montmorillonite.
Embodiment 8
Get 100 milliliters of vinyl acetates; 1 gram 1-vinyl-3-dodecyl bromination imidazole salts; the synthetic polynite of 3 grams; add in 250 milliliters the there-necked flask; install mechanical stirring; reflux condensing tube, stirring at room obtained the vinyl acetate slurry of polynite in 12 hours, and ultra-sonic dispersion is after 1 hour; add Diisopropyl azodicarboxylate 0.05 gram; stirred 1 hour, logical argon shield, oil bath is heated to 80 ℃; the limit heating; till the limit is stirred to and is fixed up, reacted 4 hours, obtain the vinyl acetate Nano composite material of montmorillonite.
Embodiment 9
50 lactan of restraining oneself, 2.5 gram natural montmorillonites, 1 gram 1; 2-dimethyl-3-(6-amino-hexadecyl) sulfuric acid imidazole salts, 6 gram hexosamines join in 250 milliliters the there-necked flask; install mechanical stirring; reflux condensing tube, logical argon shield, oil bath is heated to 100 ℃; stirred 1 hour; stop to stir, continue reaction 8 hours, prepare the nylon-6 nano composite material at 260 ℃.
0.25 the 1-methyl-3-hexadecyl Tetrafluoroboric acid imidazole salts of gram is under the 80 ℃ of vacuum-drying 6 hours, 100 ℃ of 0.5 gram Na-polynites; after the vacuum-drying 6 hours; add in the there-necked flask of 250 milliliters of exsiccant, add again and put into the exsiccant magnetic stir bar, add 100 milliliters of dry toluene that refluxed with syringe; reflux condensing tube is installed; under nitrogen protection, heating in water bath, 50 ± 2 ℃ of controlled temperature; stirred 24 hours, and obtained the slurry of organo montmorillonite.Other gets two mouthfuls of flasks of 250 milliliters of cleanings, exsiccant, put into the exsiccant magnetic stir bar, seal bottleneck with anti-mouthful of soft rubber ball, behind the pump drainage three times, extract the slurry of 50 milliliters of organo montmorillonites and inject flask, inject the isoprene of metering, adding titanium tetrachloride-triisobutyl aluminium again is catalyzer, 50 ℃ of following polymerizations 1 hour obtain cis 1,4-polyisoprene/Nano composite material of montmorillonite.
Embodiment 11
Get 100 gram ethylene glycol, 1 gram 1-vinyl-3-tetradecyl bromination imidazole salts, 4 gram Na-polynites, add in 250 milliliters the there-necked flask, install mechanical stirring, reflux condensing tube, stirring at room obtained the ethylene glycol slurry of polynite in 12 hours, behind the ultra-sonic dispersion 1 hour, add dimethyl terephthalate (DMT) 40 grams, 6 gram cobaltous acetates, 7 gram antimonous oxides are made catalyzer, stirred 1 hour, and be evacuated to 0.2MP, oil bath is heated to 190～200 ℃, the limit heating, till the limit is stirred to and is fixed up, react and obtain after 8 hours, obtain the polyethylene terephthalate Nano composite material of montmorillonite.
Embodiment 12
Get 150 milliliters of acetone, 0.5 gram 4-methyl-N-hexadecyl pyridinium bromide salt, 1.5 gram Na-polynites add in 250 milliliters the there-necked flask, and ultra-sonic dispersion obtained the acetone slurry of polynite after 3～4 hours.Add 30 gram E-51, install mechanical stirring, reflux condensing tube, stirring at room 6 hours adds 5～10 N that restrain behind the solvent of finding time, N '-dimethyl benzylamine is made solidifying agent, continue to stir 2 hours, cast progressive die tool obtains the Resins, epoxy Nano composite material of montmorillonite after the curing that heats up.
Embodiment 13
2 gram natural montmorillonites, 1 gram 4-methyl-N-dodecyl chlorination pyridinium salt, 80 gram dihydroxyl polyoxytrimethylene ethers, add in 250 milliliters the there-necked flask, stirred 6 hours, oil bath is heated to 100 ℃, stir on the limit, the limit is evacuated to 0.1MP, adds 15 gram vulcabond after 2 hours, 4 grams 1, the 4-butyleneglycol continues reaction 2～3 hours at 80～100 ℃, after removing the small molecules product, cast progressive die tool is placed in the baking oven and can obtains the urethane Nano composite material of montmorillonite after dry 24 hours.
Claims (9)
1. a montmorillonoid in-situ organises and prepares the method for nano composite polymer-montmorillonoid material, it is characterized in that, described method may further comprise the steps:
(1) imidazoles organic salt or pyridines organic salt are dissolved in the non-aqueous solvent as properties-correcting agent, stir, controlled temperature is 20 ℃～60 ℃, add polynite again, wherein the mol ratio of imidazoles organic salt or pyridines organic salt and polynite is 2: 1, stir, obtain the slurry of organo montmorillonite size of particles in nanometer range;
(2) step (1) is contained the slurry of nano organic montmorillonite particle and thermoplastic resin or rubber and carries out the in-situ solution blend, melt extrudes blend, or with the thermosetting resin crosslinking curing, obtain polynite/polymer nanocomposites;
Or
(a) imidazoles organic salt or pyridines organic salt are dissolved in the polymerization single polymerization monomer as properties-correcting agent, stir, controlled temperature is 20 ℃～60 ℃, add polynite again, wherein the mol ratio of imidazoles organic salt or pyridines organic salt and polynite is 2: 1, stir, obtain the slurry of organo montmorillonite size of particles in nanometer range;
(b) slurry that step (a) is contained the nano organic montmorillonite particle is carried out the body of the body of solution polymerization, vinyl monomer of olefinic monomer or solution polymerization, functional monomer or solution condensation polymerization, the monomeric poly-addition polymerization of synthesis of polyurethane obtains nano composite polymer-montmorillonoid material;
Described functional monomer is hexanolactam, epoxy chloropropane, dihydroxyphenyl propane, terephthalic acid, ethylene glycol, butyleneglycol, vulcabond, polyether glycol or polyester polyol.
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: described imidazoles organic salt or pyridines organic salt are the mixtures with one or more salt of following structure;
The general structure of the general 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-is selected from (1) chlorine, bromine or iodine halide anion; (2) acetate, sulfate radical or tetrafluoroborate negatively charged ion.
4. method according to claim 3 is characterized in that: further contain hydroxyl, amino substituting group in the described alkyl.
5. method according to claim 1 is characterized in that: described organic solvent is dimethylbenzene, toluene, benzene, dehydrated alcohol, anhydrous methanol, acetone, chloroform, tetracol phenixin, ethylene dichloride, Ethylene Dichloride, methyl-sulphoxide or their any mixture.
6. method according to claim 1 is characterized in that: the polynite in the described slurry that contains the nano organic montmorillonite particle and the mass percent of thermoplastic resin, rubber or thermosetting resin are 5～10: 95～90.
7. method according to claim 1 is characterized in that: described contain the nano organic montmorillonite grain in slurry in polynite and the monomeric mass percent of olefinic monomer, vinyl monomer, functional monomer or synthesis of polyurethane be 5～10: 95～90;
Described functional monomer is hexanolactam, epoxy chloropropane, dihydroxyphenyl propane, terephthalic acid, ethylene glycol, butyleneglycol, vulcabond, polyether glycol or polyester polyol.
8. according to claim 1 or 6 described methods, it is characterized in that: described thermoplastic resin is polyvinyl chloride, polyvinyl acetate (PVA), polyethylene, polypropylene, polystyrene, nitrile benzene resin, nitrile butadiene styrene resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymeric amide, polymethylmethacrylate, ethylene-propylene copolymer, butadiene-styrene block copolymer or silicone resin;
Described rubber is urethane, cis-1,4-polybutadiene rubber, chloroprene rubber, paracril, styrene-butadiene rubber(SBR), acrylic elastomer or chlorinated rubber;
Described thermosetting resin is urea aldehyde, phenolic aldehyde, epoxy or polyimide resin.
9. according to claim 1 or 7 described methods, it is characterized in that: described olefinic monomer is ethene, propylene, isoprene or divinyl;
Described vinyl monomer is vinylchlorid, vinylbenzene, methyl methacrylate, vinyl acetate or vinyl cyanide.
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| CN110229502B (en) * | 2018-03-06 | 2021-09-07 | 中国科学院化学研究所 | PA6 nano composite material and preparation method thereof |
| CN110229504B (en) * | 2018-03-06 | 2021-09-07 | 中国科学院化学研究所 | Nylon elastomer nano composite material and preparation method thereof |
| CN110229453B (en) * | 2018-03-06 | 2021-09-07 | 中国科学院化学研究所 | Thermoplastic vulcanized rubber nano composite material and preparation method thereof |
| CN109320718B (en) * | 2018-09-12 | 2020-04-07 | 中国科学院长春应用化学研究所 | High-barrier transparent flexible display material and preparation method thereof |
| CN112029089A (en) * | 2020-08-05 | 2020-12-04 | 华东理工大学 | Intercalation type poly (butyrolactam)/montmorillonite nano composite material and preparation method thereof |
| CN113968944B (en) * | 2021-11-17 | 2022-07-12 | 华南理工大学 | Organic montmorillonite modified waterborne neoprene latex and preparation process thereof |
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