CN101735667A - Sol-gel modified organic montmorillonoid and organic silicon sol-gel for modification - Google Patents
Sol-gel modified organic montmorillonoid and organic silicon sol-gel for modification Download PDFInfo
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- CN101735667A CN101735667A CN200910154771A CN200910154771A CN101735667A CN 101735667 A CN101735667 A CN 101735667A CN 200910154771 A CN200910154771 A CN 200910154771A CN 200910154771 A CN200910154771 A CN 200910154771A CN 101735667 A CN101735667 A CN 101735667A
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Abstract
The invention relates to the field of modified montmorillonite, in particular to sodium-base montmorillonoid modified by sol-gel and organic silicon sol-gel for modification as well as a preparation method. The invention discloses an organic silicon sol-gel for modification of sodium-base montmorillonite with an active functional group. The organic silicon sol-gel is prepared from organic silicon quaternary ammonium salt and organic silicon with an active functional group by a sol-gel method. The invention also discloses sol-gel modified organic montmorillonoid. The modified organic montmorillonoid is prepared in such a way that the organic silicon sol-gel is added into montmorillonoid slurry to separate and dry after cation exchange intercalation reaction. The obtained organic montmorillonoid containing different active functional groups has favorable dispersibility in a corresponding polymer and monomer and good compatibility simultaneously. The organic active montmorillonoid becomes a reinforcing agent of different polymers in 21st century and has wide application prospect in different polymer application fields.
Description
Technical field
The present invention relates to modified montmorillonite used field, relate in particular to a kind of employing collosol and gel montmorillonite modified and modification organic silicon sol gel and preparation method.
Background technology
Since the first polymkeric substance/clay nano composite material in 1986 was found, montmorillonite had become the popular object of research as one of important raw and processed materials for preparing nano material.Montmorillonite is a kind of aqueous layered struture silicate clay mineral, its unit structure cell is made up of two-layer silicon-oxy tetrahedron wafer and layer of aluminum oxygen octahedra wafer, its interlayer often adsorbs some tradable positively charged ions, the interlayer chemical micro-environment is a hydrophilic and oleophobic, because the wetting ability on montmorillonite surface, be unfavorable for that it disperses and wetting by organic phase in organic phase, for overcoming this proterties, must make the montmorillonite surface be hydrophobicity, the selection of organic modifiers is the organise key of process of montmorillonite.
When preparing the polymkeric substance montmorillonite nano-composite material at present, the modification main method to montmorillonite that is adopted has: (1) adsorption method, (2) base exchange method, (3) coupling grafting method, three kinds of methods cut both ways, and base exchange method is unusual useful method.Select suitable intercalator for use, for example use the positively charged ion (mainly being sodium ion) between organic quaternary ammonium salt positively charged ion and montmorillonite layer to carry out permutoid reaction, it is big that interlamellar spacing becomes, covered by the long alkyl chain on the organic ion owing to sheet surfaces simultaneously, changed the interlayer microenvironment, the montmorillonite surfaces externally and internally becomes lipophilicity by wetting ability, reduces the silicate surfaces energy, raising and polymeric matrix and monomeric consistency help forming nano composite polymer/laminated silicate material.
In recent years in order better to improve modification organophilic clay and organic consistency, further improve the mechanical and physical performance of organophilic clay/polymer composites simultaneously, close the quaternary ammonium salt of two keys, epoxy, amido montmorillonite is carried out organic modification by containing specific functional groups such as insatiable hunger, prepare functionalized organophilic clay, with polymer blending or carry out the matrix material that in-situ polymerization prepares mechanical and physical performance is preferably arranged, montmorillonite can better disperse in polymkeric substance simultaneously.
Summary of the invention
Exist surface hydrophilic to hate the defective of oily characteristic in order to solve montmorillonite, an object of the present invention is to provide na-montmorillonite modification organic silicon sol gel with active function groups, it carries out organic modification to montmorillonite, and the interlayer preparation that different active function groups intercalations can be entered montmorillonite contains the organic active soil of functional activity group.Another object of the present invention provides and adopts above-mentioned organic silicon sol gel montmorillonite modified, and it contains different activities functional group, has good dispersiveness in corresponding polymer and monomer, has fine consistency simultaneously.
In order to realize first above-mentioned purpose, the present invention adopts following technical scheme:
Na-montmorillonite modification organic silicon sol gel with active function groups, this organic silicon sol gel adopts organosilicon quaternary ammonium salt and the organosilicon that contains active function groups to obtain by Prepared by Sol Gel Method, and organosilicon quaternary ammonium salt is as follows respectively with the organosilyl structural formula that contains active function groups:
Organosilicon quaternary ammonium salt:
The organosilicon that contains active function groups:
Wherein, described R is a carbochain, and X is Cl, and Br or I, Re are active function groups.
The main purpose of the reaction of above-mentioned sol-gel is by organosilicon quaternary ammonium salt and the organosilyl condensation reaction that contains functional group, generate the organosilicon contain quaternary ammonium salt and organo-functional group simultaneously, the organosilicon that contains functional group by control and the mole of organosilicon quaternary ammonium salt recently realize intercalation organo-functional group how much.As preferably, above-mentioned organosilicon quaternary ammonium salt and the organosilyl mol ratio that contains active function groups are 1: 2～1: 4.
As preferably, above-mentioned R is C
nH
2n+1, described n is selected from 12,14,16 and 18.
As preferably, above-mentioned Re is selected from amido, epoxy group(ing) and (methyl) acryloxy, or be selected from and contain thermal initiator or light trigger active function groups.Re is selected from amido, and when epoxy group(ing) and (methyl) acryloxy, concrete structure respectively can be as follows:
The present invention also provides the above-mentioned modification preparation method of organic silicon sol gel, and this method comprises the steps:
1. organosilicon quaternary ammonium salt adopts following chemical equation, reacts in organic solvent, separates preparing in non-polar solvent:
Wherein, described R is a carbochain, and X is Cl, Br or I;
2. under 40～80 ℃ of conditions, the organosilicon quaternary ammonium salt that method for preparing is obtained mixes in ethanol with the functional organosilicon that contains specific functional groups, and add a spot of water, make the catalyzer of sol-gel of acid or alkali, stir afterwards, sol gel reaction makes described organic silicon sol gel.
As preferably, above-mentioned step 1. in organic solvent select for use in tetrahydrofuran (THF), methylene dichloride or the ethyl acetate, non-polar solvent adopts normal hexane.
As preferably, above-mentioned step 1. in the temperature of reaction be 20～80 ℃, the reaction times is 10 minutes to 6 hours.
The 1. middle control principle that reacts of above-mentioned step is as follows:
(1) selection of reaction scheme
To with the quaternised reaction of different chain length, reaction conditions difference.For the reaction of methyl, in tetrahydrofuran (THF) or methylene dichloride, slowly drip methyl iodide being lower than under 20 ℃ of conditions, separate that then to adopt in non-polar solvent as disperse the precipitate and separate of formation in the normal hexane promptly be product.Then in ethyl acetate, carry out for reaction than long-chain.
(2) control of temperature of reaction
To with the reaction of different chain length, temperature control is different, methyl such as methyl iodide temperature are lower than under 20 ℃ of conditions, the then temperature of chain length is high as C
16H
33The Br temperature is about 75 ℃, and in addition to different halohydrocarbon temperature differences, temperature just is followed successively by RCl＞RBr＞RI, and bulk temperature is between 20～80 ℃.
(3) control in reaction times
The overall time increases along with the increase of chain length, and the halohydrocarbon time length of identical chain length is followed successively by RCl＞RBr＞RI, and the reaction times is 10 minutes to 6 hours.For the reaction of methyl iodide, react more violent, being lower than under 20 ℃ of conditions, in tetrahydrofuran (THF) or methylene dichloride, slowly drip methyl iodide, react and got final product in 10 minutes.
In the solgel reaction process, the reaction times can not be too short, and catalyst concn can not be very little, temperature can not be too low, can cause reaction not exclusively like this, functional groups can not enter the interlayer of montmorillonite along with the organosilyl intercalation of quaternary ammonium salt, causes waste, but the reaction times can not be oversize, catalyst concn can not be too high, and temperature can not be too high, causes sol gel reaction excessive, polycondensation causes the appearance of too big condensation polymer, makes intercalation be difficult to take place.
In order to realize second above-mentioned purpose, the present invention adopts following technical scheme:
Sol-gel montmorillonite modified, this modified montmorillonoid adopt and add in na-montmorillonite slurry that the described organic silicon sol gel of above-mentioned any one technical scheme separates after by the cationic exchange intercalation and drying makes.
As preferably, the consumption of the organosilicon quaternary ammonium salt in the above-mentioned organic silicon sol gel be the montmorillonite cation exchange capacity 0.5-2 doubly.
The invention also discloses the preparation method of sol-gel montmorillonite modified, this method adopts following step: the 1. preparation of montmorillonite slurries, na-montmorillonite is dispersed in the water, and vigorous stirring prepares the montmorillonite slurries, and the montmorillonite concentration of slurry is 2%～10%; 2. the alcohol mixeding liquid with the organic silicon sol gel joins rapidly in the vigorous stirring montmorillonite slurries, prepare described sol-gel montmorillonite modified by centrifugation or pressure-filteration drying behind stirring reaction 0.5～2h, the volumetric concentration of described ethanol and water is 0.5～1.
The main lime light of the organo montmorillonite by sol-gel modification preparation have following some:
1. quaternary ammonium salt organosilicon and functional organosilyl consumption are very big to the organophilic clay quality influence, and experiment shows that the organosilyl consumption of quaternary ammonium salt is 0.5-2 a times of montmorillonite cation exchange capacity, and functional organosilyl consumption is 2～4 times of the organosilyl consumption of quaternary ammonium salt.
2. consumption of ethanol is in carrying out the solgel reaction process, amount that can be less, with save energy, but organise in the treating processes carrying out montmorillonite, the volumetric concentration that makes ethanol and water is 0.5～1, and alcohol concn is low excessively to be caused montmorillonite to stick to be group, and excessive concentration then montmorillonite is too disperseed, cause to be difficult for centrifugation and pressure-filteration drying, cause the alcoholic acid waste simultaneously.
The present invention is by the combination of sol-gel cationic exchange, and the interlayer with functional group's intercalation of different performance enters prepares the organophilic clay that contains active function groups.The organophilic clay that contains different activities functional group for preparing has good dispersiveness in corresponding polymer and monomer, has fine consistency simultaneously.Organic active soil will become different polymkeric substance strengthening agents of 21 century, has broad application prospects in different polymer application fields.
Description of drawings
Fig. 1 is the process flow sheet of sol-gel montmorillonite modified preparation of the present invention.
Fig. 2 is the TEM figure of collosol and gel modified organo montmorillonite in Resins, epoxy.
Embodiment
Embodiment 1
As shown in Figure 1,12.52g (0.05mol) isocyanate group propyl-triethoxysilicane (IPS), 50mL anhydrous ethyl acetate and 0.2g dibutyl tin laurate mixture add in the 250mL there-necked flask.Be heated to temperature when being raised to 70 ℃ under constant temperature, drip 4.46g (0.05mol) N with constant pressure funnel, N-dimethyl ethanol ammonia dropwised in about 2 hours.Continue reaction after 2 hours, slowly add 7.10g (0.05mol) methyl iodide after stopping to heat cool to room temperature, after reacting 10 minutes, after rotary evaporation is removed partial solvent, in the time of induction stirring slowly Dropwise 5 0mL anhydrous n-hexane in above-mentioned solution, the adularescent throw out is separated out immediately, dropwise the back mixture and leave standstill 3h, rotary evaporation is except that desolvating after removing upper clear supernate, add and continue Dropwise 5 0mL anhydrous n-hexane again after a small amount of anhydrous ethyl acetate makes the white precipitate dissolving, repeat the aforesaid operations process, obtain the product of needed purifying at last.Resulting white products is dissolved in the methanol solution, is mixed with 50% solution for standby.
Organosilyl 50% methanol solution of the quaternary ammonium salt of 2g montmorillonite cation exchange capacity, the Racemic glycidol propyl trimethoxy silicon of different cation exchange capacitys, the mixture of 100mL dehydrated alcohol and 1mL deionized water and 1mL 0.1N hydrochloric acid soln has added to go in the 500mL single port flask, induction stirring 24h under 50 ℃ of conditions.Change different Racemic glycidol propyl trimethoxy silicon concentrations and repeat above-mentioned reaction, make the mol ratio of quaternary ammonium salt organosilicon and Racemic glycidol propyl trimethoxy silicon be respectively 1/1,1/2,1/3,1/4 and 1/5.
Montmorillonite (2g) is dispersed in the 100mL deionized water, under 50 ℃ of conditions, stir 2h, in several minutes, the solution of quaternary ammonium salt organosilicon and Racemic glycidol propyl trimethoxy silicon sol-gel reaction is added the above-mentioned montmorillonite and the dispersion liquid of water afterwards, stir behind the 1h by centrifugation and be scattered in once more in the deionized water, carry out aforesaid operations repeatedly up to showing the existence that does not have iodide with 0.1N silver nitrate solution drop.The polynite of modification is at last at 40 ℃ of condition vacuum 24h that is dried.
With the polynite of above-mentioned modification be dispersed in Resins, epoxy TEM figure as shown in Figure 2.
Embodiment 2
Organosilyl 50% methanol solution of the quaternary ammonium salt of 1g montmorillonite cation exchange capacity, the rare acyloxy propyl-triethoxysilicane of the methyl-prop of 3 times of quaternary ammonium salt organosilicon molar weights, the mixture of 100mL dehydrated alcohol and 1mL deionized water and 2mL 0.1N hydrochloric acid soln has added to go in the 500mL single port flask, induction stirring 24h under 50 ℃ of conditions.
Montmorillonite (2g) is dispersed in the 100mL deionized water, under 50 ℃ of conditions, stir 2h, the cetyl trimethylammonium bromide that in the solution of quaternary ammonium salt organosilicon and the rare acyloxy propyl-triethoxysilicane of methyl-prop solgel reaction, adds 2g montmorillonite cation exchange capacity afterwards, with the solution of quaternary ammonium salt organosilicon and the reaction of Racemic glycidol propyl trimethoxy silicon sol-gel and add above-mentioned montmorillonite and the dispersion liquid of water, stir behind the 1h after the dissolving fully by the separation drying.
Claims (10)
1. the na-montmorillonite modification organic silicon sol gel that has active function groups, it is characterized in that this organic silicon sol gel adopts organosilicon quaternary ammonium salt and the organosilicon that contains active function groups to obtain by Prepared by Sol Gel Method, organosilicon quaternary ammonium salt is as follows respectively with the organosilyl structural formula that contains active function groups:
Organosilicon quaternary ammonium salt:
The organosilicon that contains active function groups:
Wherein, described R is a carbochain, and X is Cl, and Br or I, Re are active function groups.
2. the na-montmorillonite modification organic silicon sol gel with active function groups according to claim 1 is characterized in that: organosilicon quaternary ammonium salt is 1: 2～1: 4 with the organosilyl mol ratio that contains active function groups.
3. the na-montmorillonite modification organic silicon sol gel with active function groups according to claim 1 and 2, it is characterized in that: R is C
nH
2n+1, described n is selected from 12,14,16 and 18.
4. the na-montmorillonite modification organic silicon sol gel with active function groups according to claim 1 and 2, it is characterized in that: Re is selected from amido, epoxy group(ing) and (methyl) acryloxy, or be selected from and contain thermal initiator or light trigger active function groups.
5. the preparation method with na-montmorillonite modification of active function groups with the organic silicon sol gel according to claim 1 and 2 is characterized in that this method comprises the steps:
1. organosilicon quaternary ammonium salt adopts following chemical equation, reacts in organic solvent, separates preparing in non-polar solvent:
Wherein, described R is a carbochain, and X is Cl, Br or I;
2. under 40～80 ℃ of conditions, the organosilicon quaternary ammonium salt that method for preparing is obtained mixes in ethanol with the functional organosilicon that contains specific functional groups, and add a spot of water, make the catalyzer of sol-gel of acid or alkali, stir afterwards, sol gel reaction makes described organic silicon sol gel.
6. the preparation method with na-montmorillonite modification of active function groups with the organic silicon sol gel according to claim 5, it is characterized in that: the 1. middle organic solvent of step is selected for use in tetrahydrofuran (THF), methylene dichloride or the ethyl acetate, and non-polar solvent adopts normal hexane.
7. the preparation method with na-montmorillonite modification of active function groups with the organic silicon sol gel according to claim 5, it is characterized in that: the step 1. temperature of middle reaction is 20～80 ℃, and the reaction times is 10 minutes to 6 hours.
8. sol-gel montmorillonite modified is characterized in that: this organo montmorillonite adopts and adds in na-montmorillonite slurry that claim 1 or 2 described organic silicon sol gels separate after by the cationic exchange intercalation and drying makes.
9. sol-gel montmorillonite modified according to claim 8 is characterized in that: the consumption of the organosilicon quaternary ammonium salt in the organic silicon sol gel is 0.5-2 a times of montmorillonite cation exchange capacity.
10. the preparation method of sol-gel montmorillonite modified according to claim 8 is characterized in that this method adopts following step:
1. the preparation of montmorillonite slurries is dispersed in na-montmorillonite in the water, and vigorous stirring prepares the montmorillonite slurries, and the montmorillonite concentration of slurry is 2%～10%;
2. claim 1 or 2 described organic silicon sol gels and alcoholic acid mixed solution are joined rapidly in the vigorous stirring montmorillonite slurries, prepare described sol-gel montmorillonite modified by centrifugation or pressure-filteration drying behind stirring reaction 0.5～2h, the volume ratio of described ethanol and water is 0.5～1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380346A (en) * | 2011-08-12 | 2012-03-21 | 浙江工业大学 | Organic/inorganic flaky adsorbing material and application thereof to acidic printing and dyeing wastewater |
| CN109081659A (en) * | 2018-08-08 | 2018-12-25 | 赵丽敏 | A kind of heat insulating board and preparation method thereof with fire-proof function |
| CN111574899A (en) * | 2020-06-12 | 2020-08-25 | 湖南航天三丰科工有限公司 | Organic-inorganic hybrid antifogging coating and preparation method thereof |
| CN113372813A (en) * | 2021-05-17 | 2021-09-10 | 上海电力大学 | Preparation method of montmorillonite/sol-gel composite coating |
| CN114958316A (en) * | 2022-05-31 | 2022-08-30 | 中国石油天然气集团有限公司 | Organic soil for oil-based drilling fluid and preparation method thereof |
-
2009
- 2009-12-04 CN CN200910154771A patent/CN101735667A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380346A (en) * | 2011-08-12 | 2012-03-21 | 浙江工业大学 | Organic/inorganic flaky adsorbing material and application thereof to acidic printing and dyeing wastewater |
| CN102380346B (en) * | 2011-08-12 | 2013-11-06 | 浙江工业大学 | Organic/inorganic flaky adsorbing material and application thereof in acidic printing and dyeing wastewater |
| CN109081659A (en) * | 2018-08-08 | 2018-12-25 | 赵丽敏 | A kind of heat insulating board and preparation method thereof with fire-proof function |
| CN111574899A (en) * | 2020-06-12 | 2020-08-25 | 湖南航天三丰科工有限公司 | Organic-inorganic hybrid antifogging coating and preparation method thereof |
| CN111574899B (en) * | 2020-06-12 | 2021-09-03 | 湖南航天三丰科工有限公司 | Organic-inorganic hybrid antifogging coating and preparation method thereof |
| CN113372813A (en) * | 2021-05-17 | 2021-09-10 | 上海电力大学 | Preparation method of montmorillonite/sol-gel composite coating |
| CN113372813B (en) * | 2021-05-17 | 2022-08-23 | 上海电力大学 | Preparation method of montmorillonite/sol-gel composite coating |
| CN114958316A (en) * | 2022-05-31 | 2022-08-30 | 中国石油天然气集团有限公司 | Organic soil for oil-based drilling fluid and preparation method thereof |
| CN114958316B (en) * | 2022-05-31 | 2023-06-20 | 中国石油天然气集团有限公司 | Organic soil for oil-based drilling fluid and preparation method thereof |
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Application publication date: 20100616 |