CN101700888B - Hyper-branched exfoliated organic montmorillonoid with controllable branching coefficient and preparation method thereof - Google Patents
Hyper-branched exfoliated organic montmorillonoid with controllable branching coefficient and preparation method thereof Download PDFInfo
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- CN101700888B CN101700888B CN2009100528577A CN200910052857A CN101700888B CN 101700888 B CN101700888 B CN 101700888B CN 2009100528577 A CN2009100528577 A CN 2009100528577A CN 200910052857 A CN200910052857 A CN 200910052857A CN 101700888 B CN101700888 B CN 101700888B
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Abstract
The invention provides hyper-branched exfoliated organic montmorillonoid with a controllable branching coefficient and a preparation method thereof. The preparation method comprises the following steps: (1) dispersing the mixture of inorganic montmorillonoid, organized intercalator and ethanol water, and then collecting the solid substance therein to obtain the organic montmorillonoid, wherein the organized intercalator is dihydric quaternary ammonium salt; and (2) conducting the reaction of the organic montmorillonoid in step (1) with dicarboxyl monomers and dyhydroxyl monomers in the protective presence of N2 in non-polar solvent, then, precipitating by adding precipitator, and vacuum-drying the precipitate to obtain the hyper-branched exfoliated organic montmorillonoid with the particle size of the lamella thereof being evenly distributed in a range of 30nm to 50nm. The organic montmorillonoid of the invention has good compatibility with polymers, therefore, the organic montmorillonoid is directly applicable to the preparation of various polymers without complicated solution or melt intercalation; and the invention has the advantages of low production cost and easy implementation.
Description
Technical field
The present invention relates to a kind of hyper-branched exfoliated organic montmorillonoid and preparation method thereof.
Background technology
Polynite claims montmorillenite again, is bentonitic major ingredient.Chemical constitution is Na
0.7(Al
3.3Mg
0.7) Si
8O
20(OH)
4NH
2O belongs to 2: 1 type layered silicates, and promptly each unit cell constitutes the sandwich-like structure by carrying an alumina octahedral wafer secretly in the middle of two silicon-oxy tetrahedron wafers, connects by shared Sauerstoffatom between the two.This tetrahedron and octahedral close-packed structure make its lattice arrangement with high-sequential, and every layer thickness is 1nm, have very high rigidity, and interlayer is easy glide not.
Excellent mechanical property and cheap price make polynite become the first-selected mineral of preparation nano composite material.Chinese scholars has been carried out research to a certain degree to nano composite polymer-montmorillonoid material, and the result shows that as lamellated silicate, polynite must make it peel off, and could show the reinforcing property that it is unique fully in application process.
In recent years, because constructing of hyperbranched macromolecular uniqueness makes synthesizing of hyperbranched macromolecular worldwide be subjected to people with application and more and more pays close attention to.Compare with linear macromolecule, hyperbranched macromolecular has inner porous three-dimensional structure, and the end group that surface enrichment is a large amount of makes hyperbranched macromolecular have preferable reactive behavior.In addition, the synthetic employing " single stage method " of hyperbranched macromolecular or " accurate single stage method ", synthetic method is simple, need not loaded down with trivial details purifying consuming time and sepn process, greatly reduces cost.Therefore, hyperbranched polymer particular structure and simple synthetic method all have a wide range of applications it in a lot of fields.
Wang Jincheng etc. adopt hyperbranched technology to prepare exfoliated organic montmorillonoid at patent CN101050317, its reinforcing effect excellence in silicon rubber, but also there is certain shortcoming, that is: specifically do not set forth for the feature of ultra-branched organic montmorillonite, and adopt the degree of branching of the hyperbranched polymer of this patent preparation to be difficult to control, so the interlamellar spacing enlarged degree of gained polynite is difficult to control.
Summary of the invention
The purpose of this invention is to provide a kind of hyper-branched exfoliated organic montmorillonoid with controllable branching coefficient and preparation method thereof, to overcome the defective of current material.
The preparation method of said hyper-branched exfoliated organic montmorillonoid comprises the steps:
1. organo montmorillonite is synthetic:
The mixture of inorganic polynite, organise intercalator and aqueous ethanolic solution at 70～80 ℃ of dispersed with stirring 2～4h, is collected solid matter wherein then,, obtain organo montmorillonite in 70～90 ℃ of vacuum-drying 2～4h;
The volume ratio of ethanol and water is: ethanol: water=1: 1.4～1.6, preferred 1: 1.5;
In the aqueous ethanolic solution, the content of inorganic polynite is 1～3g/mL, and the content of the intercalator that organises is 2～6g/mL;
Said inorganic polynite can be adopted business-like product, the product of the SMP trade mark of producing as Zhejiang Feng Hong clay company limited;
The described intercalator that organises is the dihydroxyl quaternary ammonium salt, preferably double hydroxyethyl Dodecyl trimethyl ammonium chloride, two hydroxyl stearyl dimethyl benzyl ammonium chloride or two hydroxyl octadecyl trimethylammonium bromides etc., all can adopt business-like product, as the product of the limited reagent of chemistry company of Shanghai traditional Chinese medicines group;
2. hyper-branched exfoliated organic montmorillonoid is synthetic:
With step organo montmorillonite, dicarboxyl monomer and dihydroxyl monomer 1., at N
2Under the protection, in non-polar solvent, 100～150 ℃ of reaction 24～48h add the precipitation agent precipitation then, and throw out gets described hyper-branched exfoliated organic montmorillonoid at 50～70 ℃ of vacuum-drying 1～3h;
In the non-polar solvent, the content of organo montmorillonite is 5～10g/mL;
The monomeric add-on of dicarboxyl is 40～60% of a non-polar solvent volume;
The monomeric add-on of dihydroxyl is 30～50% of a non-polar solvent volume;
The add-on of precipitation agent is 5～10% of a non-polar solvent volume;
Said dicarboxyl monomer is selected from the isomer of the di-carboxylic acid of the derivative of di-carboxylic acid of homologue, C2～C10 of di-carboxylic acid of di-carboxylic acid, C2～C10 of C2～C10 or C2～C10;
Preferred di-carboxylic acid is oxalic acid, propanedioic acid, Succinic Acid, hexanodioic acid, suberic acid or sebacic acid;
Described dihydroxyl monomer is selected from the isomer of the dibasic alcohol of the derivative of dibasic alcohol of homologue, C2～C10 of dibasic alcohol of dibasic alcohol, C2～C10 of C2～C10 or C2～C10;
Preferred dihydroxyl monomer is ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, ethohexadiol or decanediol;
Described non-polar solvent is selected from chloroform, tetrahydrofuran (THF), Liquid Paraffin, vegetables oil, hexane, ether or ethyl acetate etc.;
Described precipitation agent is more than one in acetone, water, methyl alcohol or the ethanol.
The present invention passes through molecular designing, the ingenious differential responses activity of utilizing between different functional groups, with commercial dicarboxyl, dihydroxyl and the synthetic hyperbranched polymer of hydroxyl quaternary ammonium salt reaction with extensive prospect, not only can enlarge the interlamellar spacing of polynite by the chemical reaction heat that the reaction of hydrophilic radicals such as carboxyl, hydroxyl is produced, and can control the degree of branching of product by the ratio of the hydroxyl quaternary ammonium salt in dihydroxyl monomer and the organo montmorillonite, reach the purpose of preparation exfoliated organic montmorillonoid.
The present invention can adopt the degree of branching of nmr for the determination hyperbranched polymer, is solvent with the tetrahydrofuran (THF), adopts the interlamellar spacing of small-angle diffraction method test polynite, adopts transmission electron microscope method to observe the size of particles of exfoliated polynite.
Prepared hyper-branched exfoliated organic montmorillonoid, its advantage is: the size distribution of lamella is even, and particle size distribution range is 30～50nm; Consistency excellence with polymkeric substance can directly apply in all kinds of polymer processings, need not loaded down with trivial details solution or fusion intercalation, and production cost is low, easy to implement.
Embodiment
Embodiment 1
Getting the inorganic polynite of 10g and the double hydroxyethyl Dodecyl trimethyl ammonium chloride of 20g joins in the there-necked flask, and adding 10mL aqueous ethanolic solution (volume ratio of ethanol and water is 1: 1.4), be heated to 70 ℃, stir 4h, solid-liquid separation then, washing in 90 ℃ of vacuum-drying 2h, gets organo montmorillonite;
With this organo montmorillonite, oxalic acid, ethylene glycol, at N
2Under the protection, in chloroform, 100 ℃ of reaction 48h add acetone precipitation, filtration, separation, and at 50 ℃ of vacuum-drying 3h, obtain required hyper-branched exfoliated organic montmorillonoid;
In the chloroform, the content of organo montmorillonite is 5g/mL;
The add-on of oxalic acid is 40% of a chloroform volume;
The add-on of ethylene glycol is 30% of a chloroform volume;
The add-on of acetone is 5% of a chloroform volume;
The degree of branching of hyperbranched polymer, the interlamellar spacing of polynite and size thereof see Table 1.
Embodiment 2
Getting the inorganic polynite of 20g and two hydroxyl stearyl dimethyl benzyl ammonium chlorides of 40g joins in the there-necked flask, and adding 10mL aqueous ethanolic solution, (volume ratio of ethanol and water is 1: 1.5), be heated to 75 ℃, stir 3h, solid-liquid separation is washed then, in 80 ℃ of vacuum-drying 3h, get organo montmorillonite;
With this organo montmorillonite, propanedioic acid, propylene glycol, at N
2Under the protection, in tetrahydrofuran (THF), 125 ℃ of reaction 36h add methanol extraction, filtration, separation, and at 60 ℃ of vacuum-drying 2h, get required hyper-branched exfoliated organic montmorillonoid;
In the tetrahydrofuran (THF), the concentration of organo montmorillonite is 7.5g/mL;
The add-on of propanedioic acid is 50% of a tetrahydrofuran (THF) volume;
The add-on of propylene glycol is 40% of a tetrahydrofuran (THF) volume;
The add-on of methyl alcohol is 8% of a tetrahydrofuran (THF) volume;
The degree of branching of hyperbranched polymer, the interlamellar spacing of polynite and size thereof see Table 1.
Embodiment 3
Getting the inorganic polynite of 30g and the double hydroxyethyl Dodecyl trimethyl ammonium chloride of 60g joins in the there-necked flask, and adding 10mL aqueous ethanolic solution, (volume ratio of ethanol and water is 1: 1.6), be heated to 80 ℃, stir 2h, solid-liquid separation is washed then, in 70 ℃ of vacuum-drying 4h, get organo montmorillonite;
With this organo montmorillonite, Succinic Acid, butyleneglycol, at N
2Under the protection, in ether, 150 ℃ of reaction 24h add ethanol sedimentation, filtration, separation, and at 70 ℃ of vacuum-drying 1h, get required hyper-branched exfoliated organic montmorillonoid.
In the ether, the concentration of organo montmorillonite is 10g/mL;
The add-on of Succinic Acid is 60% of an ether volume;
The add-on of butyleneglycol is 50% of an ether volume;
The alcoholic acid add-on is 10% of an ether volume;
The degree of branching of hyperbranched polymer, the interlamellar spacing of polynite and size thereof see Table 1.
Table 1
| Embodiment | The degree of branching | Interlamellar spacing | Median size (nm) |
| 1 | 0.7 | Peel off | 30 |
| 2 | 0.8 | Peel off | 40 |
| 3 | 0.9 | Peel off | 50 |
Claims (6)
1. the preparation method of hyper-branched exfoliated organic montmorillonoid with controllable branching coefficient is characterized in that, comprises the steps:
1. the mixture with inorganic polynite, organise intercalator and aqueous ethanolic solution disperses, and collects solid matter wherein then, obtains organo montmorillonite;
The described intercalator that organises is double hydroxyethyl Dodecyl trimethyl ammonium chloride, two hydroxyl stearyl dimethyl benzyl ammonium chloride or two hydroxyl octadecyl trimethylammonium bromide;
The volume ratio of ethanol and water is: ethanol: water=1: 1.4～1.6, and in the aqueous ethanolic solution, the content of inorganic polynite is 1～3g/mL, the content of the intercalator that organises is 2～6g/mL;
2. step organo montmorillonite, dicarboxyl monomer and dihydroxyl monomer 1. is at N
2Protection in solvent, is reacted down, adds the precipitation agent precipitation then, and throw out vacuum-drying gets described hyper-branched exfoliated organic montmorillonoid;
In the solvent, the content of organo montmorillonite is 5～10g/mL; The monomeric add-on of dicarboxyl is 40～60% of a solvent volume; The monomeric add-on of dihydroxyl is 30～50% of a solvent volume; The add-on of precipitation agent is 5～10% of a solvent volume;
Said dicarboxyl monomer is selected from the di-carboxylic acid of C2～C10;
Described dihydroxyl monomer is selected from the dibasic alcohol of C2～C10;
Described solvent is selected from chloroform, tetrahydrofuran (THF), Liquid Paraffin, vegetables oil, hexane, ether or ethyl acetate;
Described precipitation agent is more than one in acetone, water, methyl alcohol or the ethanol.
2. method according to claim 1 is characterized in that, the mixture of inorganic polynite, organise intercalator and aqueous ethanolic solution at 70～80 ℃ of dispersed with stirring 2～4h, is collected solid matter wherein, then in 70～90 ℃ of vacuum-drying 2～4h.
3. method according to claim 1 is characterized in that, step 2. in, described organo montmorillonite, dicarboxyl monomer and dihydroxyl monomer are at N
2Under the protection, in solvent, 100～150 ℃ of reaction 24～48h add the precipitation agent precipitation then, and throw out gets described hyper-branched exfoliated organic montmorillonoid at 50～70 ℃ of vacuum-drying 1～3h.
4. method according to claim 1 is characterized in that, described di-carboxylic acid is oxalic acid, propanedioic acid, Succinic Acid, hexanodioic acid, suberic acid or sebacic acid.
5. method according to claim 4 is characterized in that, the dihydroxyl monomer is ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, ethohexadiol or decanediol.
6. according to the hyper-branched exfoliated organic montmorillonoid with controllable branching coefficient of each described method preparation of claim 1～5.
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| CN106362695B (en) * | 2016-10-04 | 2018-10-26 | 青岛大学 | A kind of quaternary ammonium salt cationic modified montmorillonoid and preparation method thereof |
| CN109019540A (en) * | 2018-08-17 | 2018-12-18 | 深圳市中科墨磷科技有限公司 | A method of preparing black phosphorus nanometer sheet |
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