CN100450923C - Preparation method of thermal stabilization organic montmorillonite - Google Patents
Preparation method of thermal stabilization organic montmorillonite Download PDFInfo
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- CN100450923C CN100450923C CNB2006101369216A CN200610136921A CN100450923C CN 100450923 C CN100450923 C CN 100450923C CN B2006101369216 A CNB2006101369216 A CN B2006101369216A CN 200610136921 A CN200610136921 A CN 200610136921A CN 100450923 C CN100450923 C CN 100450923C
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- quaternary ammonium
- ammonium salt
- montmorillonite
- polystyrene
- tetrahydrofuran
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Abstract
The invention discloses a making method of heat stable organic montmorillonite, which comprises the following steps: allocating montmorillonite with grain size less than 50um into 1%-4% suspension through secondary distilled water; stirring under indoor temperature for 24-48h; adding the same bulk of tetrahydrofuran in the suspension; stirring 2h; dripping low-molecular weight chloromethyl phenylethene or phenylethene copolymer quaternary ammonium salt into composite solution of montmorillonite suspension and tetrahydrofuran to obtain organic montmorillonite.
Description
Technical field
The present invention relates to a kind of preparation method of thermal stabilization organic montmorillonite.
Background technology
The preparation method of present organo montmorillonite, employed intercalation thing great majority are long chain quaternary, not only price comparison is expensive for this type of long chain quaternary modified montmorillonite, and thermostability is undesirable, and is poor with the consistency of polymeric matrix.Especially be applied in the polymkeric substance Nano composite material of montmorillonite that needs high processing temperature when preparing, Chang Yinqi decomposes and causes the color development and the degraded of polymeric matrix, and the cost height of the organo montmorillonite made from the long alkyl chain quaternary ammonium salt, so its range of application is limited to.In the prior art also not the method for useful chloromethylation prepare the preparation method of the quaternary ammonium salt of the quaternary ammonium salt of low-molecular-weight chloromethylated polystyrene or polystyrene as the intercalation thing of organo montmorillonite.
Summary of the invention
The object of the present invention is to provide a kind of method to prepare the preparation method of the quaternary ammonium salt of the quaternary ammonium salt of low-molecular-weight chloromethylated polystyrene or polystyrene as the intercalation thing of organo montmorillonite with chloromethylation.Make the reduction greatly of this organo montmorillonite cost, Heat stability is good, can be applied in the high Nano composite material of montmorillonite of processing temperature.
Technical scheme of the present invention may further comprise the steps:
(1) particle diameter is mixed with the suspension that massfraction is 1%-4% less than 50 microns polynite with redistilled water, at room temperature stirred 24-48 hour, in above-mentioned suspension, add isopyknic tetrahydrofuran (THF), stir 2h;
(2) quaternary ammonium salt that will show the quaternary ammonium salt of chloromethylated polystyrene that the synthetic molecular weight is 500-20000 or polystyrene was with 1.5: 1 tetrahydrofuran aqueous solution dissolving, slowly be added drop-wise in montmorillonite suspension liquid and the tetrahydrofuran (THF) mixed solution, described polynite is a sodium-based montmorillonite, contained sodium ion mol ratio is 1.1: 1 in control quaternary ammonium group and the clay, and stirring is spent the night, and leaves standstill, filter, use the tetrahydrofuran aqueous solution washing precipitation, drying and grinding gets organo montmorillonite.
The molecular weight of described existing synthetic lower molecular weight chloromethylation vinylbenzene or styrene copolymer is 500-20000, and now synthetic by existing synthetic route;
The quaternary ammonium salt of described low-molecular-weight chloromethylated polystyrene or styrene copolymer is to be quaternizing agent with the Trimethylamine 99, chloromethylated polystyrene or styrene copolymer are carried out quaternized processing, get corresponding quaternary ammonium salt, the mol ratio of Trimethylamine 99 and chloromethylated polystyrene or styrene copolymer is 2: 1.
Described polynite can be sodium-based montmorillonite, also can be for containing other clay of exchangeable cation.The adjacent crystal layer of this class clay is electronegative, therefore, is generally all adsorbing positively charged ion between the clay crystal layer, and this makes extraneous positively charged ion to exchange with inner positively charged ion.
Advantage of the present invention is: the present invention adopts the quaternary ammonium salt of chloromethylated polystyrene or the quaternary ammonium salt modified montmorillonite of polystyrene, owing to introduced phenyl ring, its thermostability is obviously improved; Cost reduces greatly, better with the consistency of other polymkeric substance, enlarged its use range, can be applied in the high Nano composite material of montmorillonite of processing temperature; And simple to operate, widely applicable, be easy to industrialization.
Embodiment
Embodiment 1:
(1) add 150g vinylbenzene, 3.5g Diisopropyl azodicarboxylate in the three-necked bottle that agitator, reflux condensing tube and thermometer are housed, the 150ml tetrahydrofuran (THF) after stirring, is warmed up to 75 ℃, reaction 2h.Behind the stopped reaction, solution is slowly poured in the 1000ml methyl alcohol, is stirred, leave standstill, discard the upper strata stillness of night, the gained solid is put into the vacuum drying oven drying to the upper strata clarification, molecular weight is 18000 vinylbenzene oligomer; In the three-necked bottle that agitator, reflux condensing tube and thermometer are housed, add 50g vinylbenzene oligomer, 50ml tetrahydrofuran (THF), after being stirred to polymer and dissolving fully, add 25ml chloromethyl ether and 5g zinc chloride, controlled temperature is at 30-33 ℃, behind the reaction 0.5h, stopped reaction is slowly poured solution in the big water gaging, and the limit bevelling stirs, filtering-depositing, with the mixing solutions repetitive scrubbing solid of first alcohol and water repeatedly, solid is put into the vacuum drying oven drying, obtain the polystyrene chloromethylation products.
(2) 50g polystyrene chloromethylation products is joined in the round bottom Erlenmeyer flask that stirring magnetic, prolong, tail gas receptor are housed, add the 100ml tetrahydrofuran (THF), stir, after treating that polymer dissolves fully, mol ratio by Trimethylamine 99 and chloromethylation vinylbenzene or styrene copolymer is 2: 1 excessive trimethylamine aqueous solutions of adding, and stirring is spent the night.After reaction stops, steaming solvent and water, the drying sub-quaternary ammonium salt that secures satisfactory grades with Rotary Evaporators.The 8.5g high molecular quaternary is dissolved in 1: 1 the tetrahydrofuran aqueous solution;
(3) particle diameter being mixed with massfraction less than 50 microns polynite with redistilled water is 4% suspension, at room temperature stirs 24-48 hour, measures the suspension of 100ml 4%, adds the 100ml tetrahydrofuran (THF), stirs 2h; The quaternary ammonium salt that dissolving is good slowly is added drop-wise in the clay, and stirring is spent the night, and leaves standstill, and filters, and uses the tetrahydrofuran aqueous solution washing precipitation, and drying gets organic modified montmorillonite.
The thermal degradation temperature of gained quaternary ammonium salt is 349 ℃, thermostability is than the hexadecyl quaternary ammonium salt in the long chain quaternary (250 ℃ of thermal degradation temperatures), improved 39.6%, the thermal degradation temperature of gained organo montmorillonite is 364 ℃, and thermostability gets polynite (thermal degradation temperature is 245 ℃) than long chain quaternary clearing house and improved 48.5%.The preparation organo montmorillonite through its sheet interlayer spacing of wide-angle X diffraction test shows greater than 8.0nm.
Embodiment 2:
Change the amount of Diisopropyl azodicarboxylate among the embodiment 1 into 7.5g, make molecular weight and be 7500 vinylbenzene oligomer, and corresponding quaternary ammonium salt.Change 4% suspension among the embodiment 1 into 2%, make organophilic clay.
Gained quaternary ammonium salt thermostability (thermal degradation temperature is 347 ℃) has improved 38.8% than long chain quaternary (hexadecyl quaternary ammonium salt thermal degradation temperature is 250 ℃), and gained organophilic clay (thermal degradation temperature is 349 ℃) thermostability gets native (thermal degradation temperature is 245 ℃) than long chain quaternary clearing house and improved 42.4%.The preparation organo montmorillonite through its sheet interlayer spacing of wide-angle X diffraction test shows greater than 8.0nm.
Embodiment 3:
Change 2% suspension among the embodiment 2 into 1%, make organophilic clay.
Gained organophilic clay (thermal degradation temperature is 346 ℃) thermostability gets native (thermal degradation temperature is 245 ℃) than long chain quaternary clearing house and has improved 41.2%.The preparation organo montmorillonite through its sheet interlayer spacing of wide-angle X diffraction test shows greater than 8.0nm.
Embodiment 4:
(1) in the three-necked bottle that agitator, reflux condensing tube and thermometer are housed, adds 135g vinylbenzene, 15g methyl methacrylate, 150ml tetrahydrofuran (THF), 7.5g Diisopropyl azodicarboxylate, after stirring, be warmed up to 75 ℃, reaction 2h.Behind the stopped reaction, solution is slowly poured in the 1000ml methyl alcohol, is stirred, leave standstill, discard the upper strata stillness of night, the gained solid is put into the vacuum drying oven drying to the upper strata clarification, molecular weight is 7200 styrene-methylmethacrylate copolymer.In the three-necked bottle that agitator, reflux condensing tube and thermometer are housed, add high-molecular copolymer, 50ml tetrahydrofuran (THF) among the 50g A, after being stirred to polymer and dissolving fully, add 25ml chloromethyl ether and 5g zinc chloride, controlled temperature is at 30-33 ℃, behind the reaction 0.5h, stopped reaction, solution is slowly poured in the big water gaging, the limit bevelling stirs, filtering-depositing, with the mixing solutions repetitive scrubbing solid of first alcohol and water repeatedly, solid is put into the vacuum drying oven drying, obtain the chloromethylation products of high-molecular copolymer.
(2) chloromethylation products with the 50g high-molecular copolymer joins in the round bottom Erlenmeyer flask that stirring magnetic, prolong, tail gas receptor are housed, add the 100ml tetrahydrofuran (THF), stir, treat that polymer dissolves fully after, add excessive trimethylamine aqueous solution, stirring is spent the night.After reaction stops, steaming solvent and water, the secure satisfactory grades quaternary ammonium salt of sub-multipolymer of drying with Rotary Evaporators.The quaternary ammonium salt of 9g high-molecular copolymer is dissolved in 1: 1 the tetrahydrofuran aqueous solution.
(3) particle diameter being mixed with massfraction less than 50 microns polynite with redistilled water is 1% suspension, measures 400ml suspension, adds the 400ml tetrahydrofuran (THF), stirs 2h.The quaternary ammonium salt that dissolving is good slowly is added drop-wise in the clay, and stirring is spent the night, and leaves standstill, and filters, and uses the tetrahydrofuran aqueous solution washing precipitation, and drying gets organic decoration soil.
Gained quaternary ammonium salt thermostability (thermal degradation temperature is 359 ℃) has improved 43.4% than long chain quaternary (hexadecyl quaternary ammonium salt thermal degradation temperature is 250 ℃), and gained organophilic clay (thermal degradation temperature is 324 ℃) thermostability gets native (thermal degradation temperature is 245 ℃) than long chain quaternary clearing house and improved 33.2%.The preparation organo montmorillonite through its sheet interlayer spacing of wide-angle X diffraction test shows greater than 8.0nm.
Embodiment 5: change the methyl methacrylate among the embodiment 4 into vinyl cyanide.Make molecular weight and be 10550 styrene-acrylonitrile copolymer, and corresponding quaternary ammonium salt.Gained quaternary ammonium salt thermostability (thermal degradation temperature is 371 ℃) has improved 48.4% than long chain quaternary (hexadecyl quaternary ammonium salt thermal degradation temperature is 250 ℃), and gained organophilic clay (thermal degradation temperature is 371 ℃) thermostability gets native (thermal degradation temperature is 245 ℃) than long chain quaternary clearing house and improved 51.4%.The preparation organo montmorillonite through its sheet interlayer spacing of wide-angle X diffraction test shows greater than 8.0nm.
Embodiment 6: change the methyl methacrylate among the embodiment 4 into acrylamide.Make molecular weight and be 5000 styrene-propene amide copolymer, and corresponding quaternary ammonium salt.Gained quaternary ammonium salt thermostability (thermal degradation temperature is 341 ℃) has improved 36.4% than long chain quaternary (hexadecyl quaternary ammonium salt thermal degradation temperature is 250 ℃), and gained organophilic clay (thermal degradation temperature is 337 ℃) thermostability gets native (thermal degradation temperature is 245 ℃) than long chain quaternary clearing house and improved 37.6%.The preparation organo montmorillonite through its sheet interlayer spacing of wide-angle X diffraction test shows greater than 8.0nm.
Embodiment 7: change the methyl methacrylate among the embodiment 4 into vinylformic acid.Make molecular weight and be 1100 styrene-propene acid copolymer, and corresponding quaternary ammonium salt.Gained quaternary ammonium salt thermostability (thermal degradation temperature is 269 ℃) has improved 7.6% than long chain quaternary (hexadecyl quaternary ammonium salt thermal degradation temperature is 250 ℃), and gained organophilic clay (thermal degradation temperature is 353 ℃) thermostability gets native (thermal degradation temperature is 245 ℃) than long chain quaternary clearing house and improved 44.1%.The preparation organo montmorillonite through its sheet interlayer spacing of wide-angle X diffraction test shows greater than 8.0nm.
Claims (3)
1. the preparation method of a thermal stabilization organic montmorillonite is characterized in that may further comprise the steps:
(1) particle diameter is mixed with the suspension that massfraction is 1%-4% less than 50 microns polynite with redistilled water, at room temperature stirred 24-48 hour, in above-mentioned suspension, add isopyknic tetrahydrofuran (THF), stir 2h;
(2) quaternary ammonium salt that will show the quaternary ammonium salt of chloromethylated polystyrene that the synthetic molecular weight is 500-20000 or polystyrene was with 1.5: 1 tetrahydrofuran aqueous solution dissolving, slowly be added drop-wise in montmorillonite suspension liquid and the tetrahydrofuran (THF) mixed solution, described polynite is a sodium-based montmorillonite, contained sodium ion mol ratio is 1.1: 1 in control quaternary ammonium group and the clay, and stirring is spent the night, and leaves standstill, filter, use the tetrahydrofuran aqueous solution washing precipitation, drying and grinding gets organo montmorillonite.
2. the preparation method of thermal stabilization organic montmorillonite according to claim 1, it is characterized in that the quaternary ammonium salt of described chloromethylated polystyrene or the quaternary ammonium salt of polystyrene are to be quaternizing agent with the Trimethylamine 99, chloromethylated polystyrene or polystyrene are carried out quaternized processing, get corresponding quaternary ammonium salt, the mol ratio of Trimethylamine 99 and chloromethylated polystyrene or polystyrene is 2: 1.
3. the preparation method of thermal stabilization organic montmorillonite according to claim 1 is characterized in that described polynite is the clay that contains exchangeable cation.
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| CN101798097B (en) * | 2010-04-09 | 2011-09-14 | 曹晓春 | Method for preparation of modified bentonite with vinyl monomer copolymer |
| CN102372274B (en) * | 2010-08-16 | 2013-03-13 | 中国水产科学研究院东海水产研究所 | Preparation method for bifunctional-modified montmorillonite dispersion liquid |
| CN110844907B (en) * | 2019-11-28 | 2022-02-22 | 中国科学院广州地球化学研究所 | Method for preparing silicon carbide nano material and silicon carbide-containing nano composite material by using clay mineral and application |
| CN116200937B (en) * | 2023-04-28 | 2023-09-01 | 江苏米格新材料股份有限公司 | Composite heat insulation felt and preparation method thereof |
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| US5336647A (en) * | 1991-11-14 | 1994-08-09 | Rheox, Inc. | Organoclay compositions prepared with a mixture of two organic cations and their use in non-aqueous systems |
| CN1161679A (en) * | 1994-12-16 | 1997-10-08 | 昆士兰大学 | Alumino-silicate derivatives |
| JP2000191925A (en) * | 1998-12-25 | 2000-07-11 | Toagosei Co Ltd | Organic and inorganic composite material |
| WO2004058874A1 (en) * | 2002-12-18 | 2004-07-15 | Bridgestone Corporation | Method for clay exfoliation, compositions therefore, and modified rubber contaiing same |
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| US5336647A (en) * | 1991-11-14 | 1994-08-09 | Rheox, Inc. | Organoclay compositions prepared with a mixture of two organic cations and their use in non-aqueous systems |
| CN1161679A (en) * | 1994-12-16 | 1997-10-08 | 昆士兰大学 | Alumino-silicate derivatives |
| JP2000191925A (en) * | 1998-12-25 | 2000-07-11 | Toagosei Co Ltd | Organic and inorganic composite material |
| WO2004058874A1 (en) * | 2002-12-18 | 2004-07-15 | Bridgestone Corporation | Method for clay exfoliation, compositions therefore, and modified rubber contaiing same |
| CN1792791A (en) * | 2005-11-23 | 2006-06-28 | 沈阳化工学院 | Process for preparing limellar stripping nano imvite |
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