CN101531373A - Active organo montmorillonite and preparation method thereof - Google Patents
Active organo montmorillonite and preparation method thereof Download PDFInfo
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- CN101531373A CN101531373A CN200910058917A CN200910058917A CN101531373A CN 101531373 A CN101531373 A CN 101531373A CN 200910058917 A CN200910058917 A CN 200910058917A CN 200910058917 A CN200910058917 A CN 200910058917A CN 101531373 A CN101531373 A CN 101531373A
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Abstract
The invention discloses an active organo montmorillonite and a preparation method thereof, wherein, the organo montmorillonite is the amino-containing active organo montmorillonite composed of Na-montmorillonite and an organic intercalation agent which intercalate in the Na-montmorillonite and is subjected to the modification of potassium phthalimide; the organic intercalation agent is an organic compound represented by R(CH2)<12-18N>(CH3)3R or R(CH2)<12-18>NH2 structural formulae, R in the formulae is chlorine atom or bromine atom. The preparation method thereof comprises the step of: subjecting the modified organic intercalation agent and the Na-montmorillonite to intercalation in a solvent at 80-120 DEG C and then to amination with hydrazine hydrate on condition that the solvent is present, in order to prepare the amino-containing active organo montmorillonite. The organo montmorillonite prepared by the invention has outstanding dispersity both in the organic solvent and in the water and can be better used for blending with other polymers to prepare a composite material. The invention can be used for the fields of plastic processing, the preparation of chemical building material, the preparation of nano material, biomedical material and cosmetics.
Description
Technical field
The present invention relates to imvite modified technical field, particularly relate to the technology of using drop cloth riel method that modification is carried out in polynite, a kind of organo montmorillonite and preparation method thereof specifically is provided.
Background technology
Polynite is a kind of natural nano material that exists, and its basic structural unit is to be clipped in two laminate structures between the silicon-oxy tetrahedron by a slice alumina octahedral.Si in the tetrahedron of polynite is often by Al
3+Substitute the Al in the octahedron
3+Often by Mg
2+, Fe
3+, Fe
2+, Li
+Deng replacement, thereby make the montmorillonite layer surface that superfluous negative charge be arranged, so polynite has certain ion-exchange capacity.And just because of these constructional features of polynite, the application of the matrix material aspect of itself and other polymkeric substance receives much attention.But when preparation polymer-montmorillonoid matrix material, because the natural montmorillonite surface-area is little, interlamellar spacing is less, has influenced its absorption property, so polynite in use, often it is carried out modification, to increase the distance between the montmorillonite layer.A kind of use alkyl quaternary ammonium salts R-N (CH is disclosed as CN1468914A
3)
3(R is for containing C for R '
12～18Alkyl, R ' is bromine atoms or chlorine atom) the modification sodium-based montmorillonite prepares the method for organo montmorillonite; CN1994882A discloses a kind of method of using the quaternary ammonium salt modified montmorillonoid of low-molecular-weight chloromethylation vinylbenzene or styrol copolymer; CN1462777A then uses epoxy oligomer and organo montmorillonite to carry out intercalation, to increase the interlamellar spacing of polynite.But the method for modifying of existing polynite mainly is to carry out intercalation with tensio-active agent and polynite, obtain lamella apart from increasing and lipophilicity enhanced organo montmorillonite, and its wetting ability is very poor, is restricted with the hydrophilic polymer blended applications.
Summary of the invention
The deficiency that exists at the imvite modified technology of prior art, purpose of the present invention aims to provide a kind of novel active organo montmorillonite and preparation method thereof, to enrich the kind of active organo montmorillonite, the polynite wetting ability that overcomes the prior art modification is poor, with deficiencies such as the hydrophilic polymer blended applications are restricted, satisfy the preparation of plastic working, chemical building material, fields such as preparation, bio-medical material and the makeup reply polynite requirement of nano material.
Active organo montmorillonite provided by the invention, be by sodium-based montmorillonite (Na-MMT) and insert its interlayer handle the amino active organo montmorillonite that contains that the organic intercalation agent of modification constitutes through potassium phthalimide, the described organic intercalation agent organic compound shown in the following general structure of serving as reasons:
R (CH
2)
12～18N (CH
3)
3R or R (CH
2)
12～18NH
2R in the general formula is chlorine atom or bromine atoms.
In active organo montmorillonite, the weight content of modification organic intercalation agent is generally 15%～35% of active organo montmorillonite weight, concrete content depends on preparation condition, the preparation condition difference, and the content of organic intercalation agent is also just different in the gained active organo montmorillonite.
Above-mentioned active organo montmorillonite can prepare by following method:
(1) organic compound, potassium phthalimide and the deionized water as organic intercalation agent carries out modified-reaction in the mode of reflux under 60～120 ℃, fully reaction prepares the modification organic intercalation agent after cooling is removed responseless organic intercalation agent and potassium phthalimide with deionized water wash;
(2) modification organic intercalation agent, sodium-based montmorillonite and solvent carry out intercalation under 80～120 ℃, and fully responseless modification organic intercalation agent is removed with solvent wash in the reaction back, prepares organic modification montmonrillonite;
(3) organic modification montmonrillonite and hydrazine hydrate, solvent carry out ammoxidation in the mode of reflux under 60～120 ℃, and fully responseless hydrazine hydrate is removed with solvent wash in the reaction back, prepares amination modified active organo montmorillonite.
In the technology of preparing scheme of above-mentioned active organo montmorillonite, in the process of preparation modification organic intercalation agent potassium phthalimide, be 1:(0.5～6 as the organic compound of organic intercalation agent and the consumption weight ratio of deionized water): (5～10); The consumption weight ratio of modification organic intercalation agent, sodium-based montmorillonite and solvent is (3～10) in the process of preparation organic modification montmonrillonite: (1～5): 100; The consumption weight ratio of organic modification montmonrillonite, hydrazine hydrate and solvent is (5～20) in the process of preparation active organo montmorillonite: (5～15): 100.
In the technology of preparing scheme of above-mentioned active organo montmorillonite, described reaction solvent and cleaning solvent are and are selected from N, a kind of in dinethylformamide (DMF), methyl-sulphoxide (DMSO) and the tetrahydrofuran (THF) (THF); Intercalation, ammoxidation and all be to react having under the stirring condition as the organic compound modified-reaction of intercalator; Intercalation is removed responseless modification organic intercalation agent with solvent wash after having carried out 2～6 hours, ammoxidation is removed responseless hydrazine hydrate with solvent wash after reaction has been carried out 2～6 hours; Carried out removing responseless organic intercalation agent and potassium phthalimide with deionized water wash after 4～12 hours as the organic compound modified-reaction of intercalator.
The invention discloses a kind of novel active organo montmorillonite and preparation method thereof, the organo montmorillonite that contains active amino of gained has not only increased the interlamellar spacing of polynite, and good dispersiveness is arranged all in organic solvent and water, can be used for better preparing matrix material with other polymer blendings, can enlarge the Application Areas of polynite in the preparation of plastic working, chemical building material, the field widespread uses such as preparation, bio-medical material neck and makeup of nano material.
Active organo montmorillonite provided by the invention has the positive technique effect and the advantage of following aspect more specifically:
(1) organically-modified by to Na-MMT increased the distance between the montmorillonite layer, enlarged the range of application of polynite.
(2) organo montmorillonite of the present invention's preparation is a kind of nano-scale particle, has a lot of character of nano material.
(3) organo montmorillonite of the present invention's preparation has active amino, and increase organo montmorillonite and other are the possibility of heteropolymer reaction more.
(4) therefore the organo montmorillonite of the present invention preparation has good wetting ability owing to have active amino, can be well hydrophilic and hydrophobic material blend prepares matrix material with other.
The present invention also has the advantage of some other aspect.
Embodiment
Below in conjunction with embodiment the present invention is specifically described, so that the understanding of the present invention.Be necessary what this particularly pointed out to be; embodiment is used for just that the present invention will be further described; can not be interpreted as limiting the scope of the invention; affiliated art skilled person; improvement and the adjustment of the specific embodiment of the present invention being made non-intrinsically safe according to the invention described above content are not difficulty, and such improvement and adjustment should still belong to protection scope of the present invention.
In the following embodiments, except that specifying, related component percentages all is weight percentage, and related component parts number average is parts by weight.
Embodiment 1
With the potassium phthalimide of 10 weight parts and the Cl (CH of 15 weight parts
2)
12N (CH
3)
3Cl adds in the reactor that agitator and thermometer are housed, in reactor, add the deionized water of 75 weight parts then, about 6 hours of 100 ℃ of left and right sides heated and stirred back flow reaction, use the deionized water repetitive scrubbing after being cooled to 20 ℃, remove responseless organic intercalation agent Cl (CH
2)
12N (CH
3), Cl and potassium phthalimide obtain the organic intercalation agent product of modification.
The sodium-based montmorillonite (Na-MMT) of 1 weight part and the modification organic intercalation agent product of 3 weight parts are added in the reactor that agitator and thermometer are housed, add the DMF of 96 weight parts then, about 4 hours of 120 ℃ of left and right sides stirring reactions, use the DMF repetitive scrubbing afterwards, remove responseless modification organic intercalation agent, obtain the organic modification montmonrillonite product.
The organic modification montmonrillonite of 5 weight parts and the hydrazine hydrate of 10 weight parts are added in the reactor that has agitator and thermometer, add the DMSO of 85 weight parts then, in about 6 hours of 80 ℃ of left and right sides stirring heating back flow reaction, remove responseless hydrazine hydrate with the DMSO repetitive scrubbing afterwards, obtain containing amino active organo montmorillonite product.
Embodiment 2
With the potassium phthalimide of 10 weight parts and the Br (CH of 30 weight parts
2)
18N (CH
3)
3Br adds in the reactor that agitator and thermometer are housed, in reactor, add the deionized water of 60 weight parts then, about 10 hours of 80 ℃ of left and right sides heated and stirred back flow reaction, be cooled to about 25 ℃ the back and use the deionized water repetitive scrubbing, remove responseless organic intercalation agent Br (CH
2)
18N (CH
3)
3Br and potassium phthalimide obtain the organic intercalation agent product of modification.
The sodium-based montmorillonite Na-MMT of 1 weight part and the modification organic intercalation agent product of 9 weight parts are added in the reactor that agitator and thermometer are housed, add the DMSO of 90 weight parts then, about 6 hours of 90 ℃ of left and right sides stirring reactions, use the DMSO repetitive scrubbing afterwards, remove responseless modification organic intercalation agent, obtain the organic modification montmonrillonite product.
The organic modification montmonrillonite of 5 weight parts and the hydrazine hydrate of 15 weight parts are added in the reactor that has agitator and thermometer, add the THF of 80 weight parts then, in 100 ℃ of left and right sides stirring heating back flow reaction 3 hours, remove responseless hydrazine hydrate with the THF repetitive scrubbing afterwards, get the finished product of the present invention and contain amino organo montmorillonite.
Claims (10)
1, a kind of active organo montmorillonite, it is characterized in that by sodium-based montmorillonite and insert its interlayer handle the amino active organo montmorillonite that contains that the organic intercalation agent of modification constitutes through potassium phthalimide, the described organic intercalation agent organic compound shown in the following general structure of serving as reasons:
R (CH
2)
12～18N (CH
3)
3R or R (CH
2)
12～18NH
2
R in the general formula is chlorine atom or bromine atoms.
2, active organo montmorillonite according to claim 1, the weight content that it is characterized in that organic intercalation agent is 15%～35%.
3, the preparation method of claim 1 or 2 described active organo montmorillonites is characterized in that mainly may further comprise the steps:
(1) organic compound, potassium phthalimide and the deionized water as organic intercalation agent carries out modified-reaction in the mode of reflux under 60～120 ℃, fully reaction prepares the modification organic intercalation agent after cooling is removed responseless organic intercalation agent and potassium phthalimide with deionized water wash;
(2) modification organic intercalation agent, sodium-based montmorillonite and solvent carry out intercalation under 80～120 ℃, and fully responseless modification organic intercalation agent is removed with solvent wash in the reaction back, prepares organic modification montmonrillonite;
(3) organic modification montmonrillonite and hydrazine hydrate, solvent carry out ammoxidation in the mode of reflux under 60～120 ℃, and fully responseless hydrazine hydrate is removed with solvent wash in the reaction back, prepares amination modified active organo montmorillonite.
4, the preparation method of active organo montmorillonite according to claim 3 is characterized in that in the process of preparation modification organic intercalation agent potassium phthalimide, is 1:(0.5～6 as the organic compound of organic intercalation agent and the consumption weight ratio of deionized water): (5～10).
5, the preparation method of active organo montmorillonite according to claim 3 is characterized in that the consumption weight ratio of modification organic intercalation agent, sodium-based montmorillonite and solvent in the process of preparation organic modification montmonrillonite is (3～10): (1～5): 100.
6, the preparation method of active organo montmorillonite according to claim 3 is characterized in that the consumption weight ratio of organic modification montmonrillonite, hydrazine hydrate and solvent in the process of preparation active organo montmorillonite is (5～20): (5～15): 100.
7, according to the preparation method of claim 3 or 5 or 6 described active organo montmorillonites, its feature is at described reaction solvent and cleaning solvent and is selected from a kind of among DMF, DMSO and the THF.
8,, it is characterized in that intercalation, ammoxidation and organic intercalation agent modified-reaction all are to react having under the stirring condition according to the preparation method of claim 3 or 4 or 5 or 6 described active organo montmorillonites.
9, the preparation method of active organo montmorillonite according to claim 7, it is characterized in that intercalation removes responseless modification organic intercalation agent with solvent wash after carrying out 2～6 hours, ammoxidation is removed responseless hydrazine hydrate with solvent wash after reaction is carried out 2～6 hours.
10,, it is characterized in that the organic intercalation agent modified-reaction carries out removing responseless organic intercalation agent and potassium phthalimide with deionized water wash after 4～12 hours according to the preparation method of claim 3 or 4 described active organo montmorillonites.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100589176A CN101531373B (en) | 2009-04-13 | 2009-04-13 | Active organo montmorillonite and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100589176A CN101531373B (en) | 2009-04-13 | 2009-04-13 | Active organo montmorillonite and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101531373A true CN101531373A (en) | 2009-09-16 |
| CN101531373B CN101531373B (en) | 2010-12-08 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948116A (en) * | 2010-08-16 | 2011-01-19 | 山东大学 | Method for improving dispersibility of organic soil |
| CN107141842A (en) * | 2017-06-17 | 2017-09-08 | 郑州西利康新材料有限公司 | A kind of method for improving silicon carbide micro-powder dispersiveness |
| CN111793257A (en) * | 2020-07-25 | 2020-10-20 | 穆山燕 | Packaging material and manufacturing method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208400C (en) * | 2001-11-07 | 2005-06-29 | 烟台华实科技开发有限公司 | Hydrophilic nano montmorillonoid and its prepn |
| CN1253514C (en) * | 2003-06-10 | 2006-04-26 | 上海氯碱化工股份有限公司 | Prepn of organic montmorillonoid |
-
2009
- 2009-04-13 CN CN2009100589176A patent/CN101531373B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948116A (en) * | 2010-08-16 | 2011-01-19 | 山东大学 | Method for improving dispersibility of organic soil |
| CN101948116B (en) * | 2010-08-16 | 2013-01-02 | 山东大学 | Method for improving dispersibility of organic soil |
| CN107141842A (en) * | 2017-06-17 | 2017-09-08 | 郑州西利康新材料有限公司 | A kind of method for improving silicon carbide micro-powder dispersiveness |
| CN107141842B (en) * | 2017-06-17 | 2018-11-06 | 郑州西利康新材料有限公司 | A method of improving silicon carbide micro-powder dispersibility |
| CN111793257A (en) * | 2020-07-25 | 2020-10-20 | 穆山燕 | Packaging material and manufacturing method thereof |
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| CN101531373B (en) | 2010-12-08 |
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Granted publication date: 20101208 Termination date: 20110413 |