CN100381506C - Production of nanometer imvite water-phase intercalation - Google Patents
Production of nanometer imvite water-phase intercalation Download PDFInfo
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- CN100381506C CN100381506C CNB2004100098379A CN200410009837A CN100381506C CN 100381506 C CN100381506 C CN 100381506C CN B2004100098379 A CNB2004100098379 A CN B2004100098379A CN 200410009837 A CN200410009837 A CN 200410009837A CN 100381506 C CN100381506 C CN 100381506C
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Abstract
The present invention relates to a preparing method for a nanometer montmorillonite water-phase intercalation. The method comprises: nanometer montmorillonite is stirred in water at a high speed in an ultrasonic mode to form a stable suspension system to be settled and hydrated; then, the product is stirred at 50 to 85 DEG C, and the water solution of an intercalator is added to be stirred at a high speed in an ultrasonic mode; polyvinyl alcohol which is a water-soluble macromolecule surfactant is added to be stirred at 50 to 85 DEG C and is centrifugated and dried in a freezing mode to obtain the loose montmorillonite with interlamellar spacing greater than 1.9 nanometers. The method provided by the present invention is characterized in that the polyvinyl alcohol (PVA) which is a water-soluble macromolecule surfactant is used in a water phase for implement intercalation to the montmorillonite. The method is characterized in that DMF used in the prior art is eliminated, and loose powder can be directly obtained. Consequently, the storage performance and dispersion performance during reuse of the product can be improved, which is convenient to bulk production, storage and transportation. In addition, the method of the present invention is simple, and costs are further reduced.
Description
Technical field
The present invention relates to a kind of preparation method of nano imvite water intercalation.
Background technology
Nano imvite, also be referred to as nanoclay, because itself and polymer-based carbon body interface have the ideal adhesive property, and two kinds of material coefficient of thermal expansion coefficients also are complementary, thereby the matrix material of nano imvite and polymkeric substance can be stable existence, and the introducing of nano imvite, make that the material properties such as mechanical strength, Young's modulus and heat-drawn wire of polymer materials are significantly improved, obtain the mechanical property and the resistance toheat of desired excellence.
In the applicant's ZL 01109463.x patent, a kind of method for preparing nano imvite/Aethoxy Sklerol or polyesterols matrix material is disclosed, this method is easy and simple to handle, with low cost.But the product that this method obtains is when practical application, though can make polynite in urethane, realize peeling off, can be in its preparation method process nano imvite be stored among the DMF before monomer mixes, because the intermiscibility of DMF and other solvent system is not satisfactory, and have high boiling point, be difficult for removing, so, just impracticable for the nano montmorillonite composite material that this method of other solvent systems obtains, also be not easy to simultaneously store and produce in batches.
Summary of the invention
The objective of the invention is to overcome in the prior art for preparing nano montmorillonite composite material process, nano imvite exists in the mode of DMF suspension always, and make it not satisfactory with the intermiscibility of other solvent system in application, be not easy to the defective that stores and produce in batches, thereby a kind of preparation method who does not use the nano imvite water intercalation of DMF is provided.
The objective of the invention is to realize by the following technical solutions:
The preparation method of nano imvite water intercalation provided by the invention comprises following step:
1) with cation exchange capacity is 50～200 milligramequivalents/per 100 grams, interlamellar spacing is that 20～40 parts of the nano imvites of 2～6 are that 50～85 ℃ water high speed stirs 30～1000 parts of temperature, ultrasonic 0.4～3 hour, form stable suspension system, left standstill aquation 10～48 hours;
2) suspension system that step 1) is obtained stirred 0.5～3 hour down at 50～85 ℃, then with 0.1～10 part of intercalator
In 5～20 parts of water, join in this suspension system after the dissolving, 50～90 ℃ of following high-speed stirring 0.5～5 hour, ultrasonic again 0.5～3 hour;
3) to step 2) to add molecular weight in the suspension system that obtains be 10
3～10
100.1～10 part of polyvinyl alcohol (PVA), stirred 2～6 hours down at 50～85 ℃;
4) suspension system that step 3) is obtained is centrifugal, removes the supernatant liquid postlyophilization, obtains the polynite of the interlamellar spacing of loose dress greater than 1.9 nanometers.
The nano imvite of described step 1) contains 85～93wt% montmorillonite silico-aluminate, and granularity is 30～80 microns.
Described step 2) intercalator is long chain alkyl ammonium salt or hexanodioic acid two amine salt, preferred C
16～C
18Alkyl quaternary ammonium salts, more preferred cetyl trimethylammonium bromide (CTAB).
Method provided by the invention is at aqueous phase, and use water-soluble polymer tensio-active agent---polyvinyl alcohol (PVA) carries out the novel method of intercalation to polynite.This method has been abandoned the DMF that uses in the prior art, can directly obtain loose powdered, thereby has improved the storge quality of product, and the dispersing property when reusing, and is convenient to produce in batches, stores and transportation; And method of the present invention is more simple, and cost also further reduces.
The polynite that the present invention makes is the loose powder shape, and interlamellar spacing is greater than 1.9 nanometers, and is the same with method among the 01109463.x, and can be used for all kinds of SOLVENTS system.When being used for the preparation of nano montmorillonite/polyurethane matrix material, can directly apply to the synthetic and manufacture field of existing urethane, need not change existing operating procedure and synthetic route, do not need to add other equipment yet, can directly apply to solution polymerization, synthetic as spandex silk, coating and other elastomericss, and can directly apply to the scorification polymerization.
Embodiment
Embodiment 1,
20 parts of water high speeds at 30 parts 50 ℃ of nano imvite are stirred, ultrasonic 0.4 hour, form stable suspension system, left standstill aquation 10 hours, the cation exchange capacity of this nano imvite is 50 milligramequivalents/per 100 grams, interlamellar spacing is 2 , contains 85wt% montmorillonite silico-aluminate, and granularity is 30 microns.
The suspension system that obtains was stirred 3 hours down at 50 ℃, then intercalator cetyl trimethylammonium bromide (CTAB) is joined in this suspension system after the dissolving in 5 parts of water for 0.1 part, 50 ℃ of following high-speed stirring 5 hours, ultrasonic again 3 hours.
Adding molecular weight in this suspension system is 10
310 parts of polyvinyl alcohol (PVA), stirred 6 hours down at 50 ℃; Centrifugal, remove the supernatant liquid postlyophilization, obtain of the polynite of the interlamellar spacing of loose dress greater than 1.9 nanometers.
Embodiment 2,
40 parts of water high speeds at 1000 parts 85 ℃ of nano imvite are stirred, ultrasonic 3 hours, form stable suspension system, left standstill aquation 48 hours, the cation exchange capacity of this nano imvite is 200 milligramequivalents/per 100 grams, interlamellar spacing is 6 , contains 93wt% montmorillonite silico-aluminate, and granularity is 80 microns.
The suspension system that obtains was stirred 0.5 hour down at 85 ℃, then intercalator hexanodioic acid diamines sodium is joined in this suspension system after the dissolving in 20 parts of water for 10 parts, 90 ℃ of following high-speed stirring 0.5 hour, ultrasonic again 0.5 hour.
Adding molecular weight in this suspension system is 10
100.1 part of polyvinyl alcohol (PVA), stirred 2 hours down at 85 ℃; Centrifugal, remove the supernatant liquid postlyophilization, obtain of the polynite of the interlamellar spacing of loose dress greater than 1.9 nanometers.
Embodiment 3,
30 parts of water high speeds at 200 parts 70 ℃ of nano imvite are stirred, ultrasonic 2 hours, form stable suspension system, left standstill aquation 20 hours, the cation exchange capacity of this nano imvite is 150 milligramequivalents/per 100 grams, interlamellar spacing is 4 , contains 90wt% montmorillonite silico-aluminate, and granularity is 60 microns.
The suspension system that obtains was stirred 2 hours down at 70 ℃, then intercalator octadecyl trimethylammonium bromide is joined in this suspension system after the dissolving in 12 parts of water for 3 parts, 70 ℃ of following high-speed stirring 2 hours, ultrasonic again 1 hour.
Adding molecular weight in this suspension system is 10
54 parts of polyvinyl alcohol (PVA), stirred 5 hours down at 60 ℃; Centrifugal, remove the supernatant liquid postlyophilization, obtain of the polynite of the interlamellar spacing of loose dress greater than 1.9 nanometers.
Claims (5)
1. the preparation method of a nano imvite water intercalation comprises following step:
1) with cation exchange capacity is 50～200 milligramequivalents/per 100 grams, interlamellar spacing is that 20～40 parts of the nano imvites of 2～6 are that 50～85 ℃ water high speed stirs 30～1000 parts of temperature, ultrasonic 0.4～3 hour, form stable suspension system, left standstill aquation 10～48 hours;
2) suspension system that step 1) is obtained stirred 0.5～3 hour down at 50～85 ℃, then intercalator is joined in this suspension system after the dissolving in 5～20 parts of water for 0.1～10 part, and 50～90 ℃ of following high-speed stirring 0.5～5 hour, ultrasonic again 0.5～3 hour; Described intercalator is long chain alkyl ammonium salt or hexanodioic acid two amine salt;
3) to step 2) add 0.1～10 part of polyvinyl alcohol in the suspension system that obtains, stirred 2～6 hours down at 50～85 ℃;
4) suspension system that step 3) is obtained is centrifugal, removes the supernatant liquid postlyophilization, obtains the polynite of the interlamellar spacing of loose dress greater than 1.9 nanometers.
2. the preparation method of nano imvite water intercalation as claimed in claim 1 is characterized in that, the nano imvite of described step 1) contains 85～93wt% montmorillonite silico-aluminate, and granularity is 30～80 microns.
3. the preparation method of nano imvite water intercalation as claimed in claim 1 is characterized in that, described step 2) long chain alkyl ammonium salt be C
16～C
18Alkyl quaternary ammonium salts.
4. as the preparation method of claim 1 or 3 described nano imvite water intercalations, it is characterized in that described step 2) long chain alkyl ammonium salt be cetyl trimethylammonium bromide.
5. the preparation method of nano imvite water intercalation as claimed in claim 1 is characterized in that, the molecular weight of the polyvinyl alcohol of described step 3) is 10
3～10
10
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| CNB2004100098379A CN100381506C (en) | 2004-11-22 | 2004-11-22 | Production of nanometer imvite water-phase intercalation |
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| CNB2004100098379A CN100381506C (en) | 2004-11-22 | 2004-11-22 | Production of nanometer imvite water-phase intercalation |
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| CN100381506C true CN100381506C (en) | 2008-04-16 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058678B (en) * | 2007-05-29 | 2013-03-13 | 株洲时代新材料科技股份有限公司 | Large interlamellar spacing and high activity modified calcium-base montmorillonite and preparation method thereof |
| CN101781478B (en) * | 2010-01-08 | 2012-12-05 | 中国地质大学（北京） | Carbon/montmorillonite composite nano-powder and preparation method thereof |
| CN102181114B (en) * | 2011-01-25 | 2013-04-17 | 李景峰 | Polyvinyl alcohol/smectite composite nano foamed material and preparation method thereof |
| CN102219231B (en) * | 2011-05-10 | 2013-06-19 | 中国地质大学（北京） | Cationic-nonionic composite organic montmorillonite and preparation method thereof |
| CN102241403B (en) * | 2011-05-10 | 2013-03-13 | 中国地质大学（北京） | Anionic-cationic composite intercalation type organic montmorillonite material and preparation method thereof |
| CN102816460A (en) * | 2011-06-08 | 2012-12-12 | 广达电脑股份有限公司 | Preparation method for organic montmorillonite |
| CN108002922A (en) * | 2017-12-28 | 2018-05-08 | 台州泰捷化工科技有限公司 | One heavy metal species soil-repairing agent |
| CN109853070B (en) * | 2019-02-28 | 2021-06-15 | 陕西师范大学 | Montmorillonite/polyvinyl alcohol composite flame-retardant fiber |
| CN112111995B (en) * | 2020-09-17 | 2021-10-15 | 西安交通大学 | Preparation method of montmorillonite modified transformer insulation paper |
| CN113387610B (en) * | 2021-06-24 | 2022-09-20 | 武汉理工大学 | Montmorillonite substrate layer material with function of improving fracture resistance of cement mortar and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62241880A (en) * | 1986-04-11 | 1987-10-22 | 松下電工株式会社 | Manufacture of inorganic layer porous body |
| US6262162B1 (en) * | 1999-03-19 | 2001-07-17 | Amcol International Corporation | Layered compositions with multi-charged onium ions as exchange cations, and their application to prepare monomer, oligomer, and polymer intercalates and nanocomposites prepared with the layered compositions of the intercalates |
| CN1417266A (en) * | 2001-11-07 | 2003-05-14 | 烟台华实科技开发有限公司 | Hydrophilic nano montmorillonoid and its prepn |
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2004
- 2004-11-22 CN CNB2004100098379A patent/CN100381506C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62241880A (en) * | 1986-04-11 | 1987-10-22 | 松下電工株式会社 | Manufacture of inorganic layer porous body |
| US6262162B1 (en) * | 1999-03-19 | 2001-07-17 | Amcol International Corporation | Layered compositions with multi-charged onium ions as exchange cations, and their application to prepare monomer, oligomer, and polymer intercalates and nanocomposites prepared with the layered compositions of the intercalates |
| CN1417266A (en) * | 2001-11-07 | 2003-05-14 | 烟台华实科技开发有限公司 | Hydrophilic nano montmorillonoid and its prepn |
Non-Patent Citations (1)
| Title |
|---|
| Poly(vinyl alcohol) ...... and Organoclays. Jin-Hae Chang et al.Journal of Applied Polymer Science,Vol.90 . 2003 * |
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