CN107814925A - A kind of preparation method of montmorillonite/polyphenylene oxide nano composite material - Google Patents
A kind of preparation method of montmorillonite/polyphenylene oxide nano composite material Download PDFInfo
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- CN107814925A CN107814925A CN201711129804.1A CN201711129804A CN107814925A CN 107814925 A CN107814925 A CN 107814925A CN 201711129804 A CN201711129804 A CN 201711129804A CN 107814925 A CN107814925 A CN 107814925A
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- montmorillonite
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- polyphenylene oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a kind of montmorillonite/polyphenylene oxide nano composite material and preparation method thereof, montmorillonite is first carried out hydrophobically modified by the material, then the method for using in-situ polymerization, is prepared using modified montmorillonoid as core, and polyphenylene oxide is montmorillonite/polyphenylene oxide nano composite material of shell.The material mechanical performance, processability, heat resistance, anti-flammability and excellent smell, it can be used widely in electric, electronic equipment part, vehicle arrangement part, and chemical device part, or even ship, bridge, building materials, packaging for foodstuff.
Description
Technical field
The present invention relates to a kind of preparation method of montmorillonite/polyphenylene oxide nano composite material.
Background technology
In recent years, as various equipment develop towards to mould Dai Gang lightweight direction, have high-fire resistance, anti-flammability and
Material prepared by the polyphenylene oxide resin of chemical resistance, more and more apply and set in various electric, electronic equipment parts, vehicle
Standby part, and in chemical device part, or even ship, bridge, building materials.
Polyphenylene oxide resin has good mechanical property, electrical property, heat resistance, anti-flammability and chemical stability etc., but
It is that stress cracking easily occurs for polyphenylene oxide product, notch impact strength is low, it will usually toughener is added to improve, and inflammable increasing
Tough dose of addition can cause the reduction of polyphenylene oxide fire resistance, need to add expensive fire retardant to improve fire resistance, because
On the one hand this causes cost higher, on the other hand cause the reduction of mechanical property and heat distortion temperature.In addition, polyphenylene oxide melt glues
Degree is high, processability extreme difference, it is impossible to be molded using injecting method, while smell is larger, greatly limit its application.Montmorillonite is one
The clay mineral of zeopan containing Shuifu County of kind layer chain structure, for its monocrystalline in threadiness, a diameter of 20nm or so, length is reachable
Several microns, it is a kind of natural monodimension nanometer material, there is specific diameter and duct, larger interior external surface area, spy
Different distribution of charges, containing the ignition-proof element such as magnalium and water, good colloidal property, nontoxic and larger draw ratio the features such as,
Extensive utilization has been obtained in reinforcement, nanometer toughness reinforcing, heat-resisting, fire-retardant, taste removal etc..
Further to improve mechanical property, processability, heat resistance, anti-flammability and the smell of polyphenylene oxide, and reduce cost.Adopt
With the method for in-situ polymerization, prepare using modified montmorillonoid as core, polyphenylene oxide is montmorillonite/polyphenylene oxide nano composite material of shell.
At present, this method has no document report.
The content of the invention
It is an object of the invention to provide the illiteracy of a kind of mechanical property, processability, heat resistance, anti-flammability and excellent smell to take off
Soil/polyphenylene oxide nano composite material.
Realizing the technical scheme of above-mentioned purpose is：Montmorillonite is first subjected to hydrophobically modified, then using the side of in-situ polymerization
Method, prepare using modified montmorillonoid as core, polyphenylene oxide is montmorillonite/polyphenylene oxide nano composite material of shell.
Concrete operation step of the present invention is as follows：
1st, the preparation of montmorillonite slurry：Montmorillonite powder is distributed in water and is configured to montmorillonite slurry, wherein montmorillonite
Mass ratio with water is 0.05~0.25：1；
2nd, the chemical modification of montmorillonite：It is stirred continuously down, modifying agent is added dropwise into montmorillonite slurry, wherein modifying agent is with covering
The mass ratio for taking off soil is 0.05~0.4：1, reaction temperature is 40~100 DEG C, and the reaction time is 1~24h.Filter, wash after reaction
Wash, in 60~120 DEG C of crushed after being dried, obtain modified montmorillonoid；
3rd, the preparation of modified montmorillonoid slurry：Modified montmorillonoid is distributed in organic solvent and is configured to modified montmorillonoid slurry
The mass ratio of body, wherein modified montmorillonoid and organic solvent is 0.01~0.25：1；
4th, the preparation of montmorillonite/polyphenylene oxide nano composite material：Cuprous halide, organic amine are put into modified montmorillonoid slurry
In, it is stirred continuously, then 2,6- xylenols and oxidant is dissolved in organic solvent, is added to the modification containing copper-amine complex
In montmorillonite slurry, 1~24h is reacted.Reaction solution is poured into precipitation of polyphenylene ether in the methanol solution containing 5% hydrochloric acid after reaction, taken out
Filter, is washed with the methanol solution containing 5% hydrochloric acid, then be dry, pulverize again at 50~120 DEG C, is obtained montmorillonite/polyphenylene oxide nanometer
Composite.
Modifying agent described in step 2 is silane coupler, one kind in cationic surfactant.
Organic solvent described in step 3 is 1,4- dioxane, one kind in methanol, toluene, dimethylbenzene.
Cuprous halide described in step 4 is stannous chloride, one kind in cuprous bromide, cuprous iodide.
Organic amine described in step 4 is dimethylamine, one kind in n-butylamine, pyridine, aniline.
The mass ratio of 2,6- xylenols and montmorillonite described in step 4 is 1~100：1.
The mass ratio of cuprous halide and 2,6- xylenols described in step 4 is 0.005~0.1：1.
The mass ratio of organic amine and 2,6- xylenols described in step 4 is 0.005~0.1：1.
Oxidant described in step 4 is oxygen, one kind in hydrogen peroxide, ammonium persulfate.
The mol ratio of oxidant and 2,6- xylenols described in step 4 is 0.2~1：1.
The beneficial effects of the invention are as follows：
1st, the presence of core shell structure of the present invention, uniformly montmorillonite can be uniformly dispersed, so as to most fully show its nanometer
Effect, the mechanical property in polyphenylene oxide are showed the most obvious with nanometer toughness reinforcing.
2nd, nucleome of the present invention is modified montmorillonoid, is monodimension nanometer material, has larger draw ratio, can be in polyphenylene oxide
Play strengthening action.
3rd, montmorillonite is preferable with the compatibility of polyphenylene oxide by modifier modification in the present invention, is advantageous to its mechanical property
Lifting.
4th, nucleome of the present invention is modified montmorillonoid, has higher heat resistance, therefore the heat resistance of the present invention also obtains
To raising.
5th, nucleome of the present invention is modified montmorillonoid, containing the ignition-proof element such as magnalium and water in montmorillonite, siliceous nitrogen in modifying agent
Fire resistance Deng ignition-proof element, therefore the present invention can be improved.
6th, nucleome of the present invention is modified montmorillonoid, has larger interior external surface area, special distribution of charges, energy of adsorption
Power is strong, can effectively reduce polyphenylene oxide in smell caused by processing.
Embodiment
Embodiment 1：
1st, the preparation of montmorillonite slurry：Montmorillonite powder is distributed in water and is configured to montmorillonite slurry, wherein montmorillonite
Mass ratio with water is 0.05：1；
2nd, the chemical modification of montmorillonite：It is stirred continuously down, KH550 is added dropwise into montmorillonite slurry, wherein KH550 is de- with covering
The mass ratio of soil is 0.05：1, reaction temperature is 40 DEG C, reaction time 1h.Filter, wash after reaction, powder after being dried at 60 DEG C
It is broken, obtain modified montmorillonoid；
3rd, the preparation of modified montmorillonoid slurry：Modified montmorillonoid is distributed in methanol and is configured to modified montmorillonoid slurry,
Wherein the mass ratio of modified montmorillonoid and methanol is 0.01：1；
4th, the preparation of montmorillonite/polyphenylene oxide nano composite material：Cuprous bromide, dimethylamine amine are put into modified montmorillonoid slurry
In body, it is stirred continuously, then 2,6- xylenols is dissolved in methanol, changing containing copper-amine complex is added in the case where oxygen is passed through
Property montmorillonite slurry in, react 1h.Reaction solution is poured into precipitation of polyphenylene ether in the methanol solution containing 5% hydrochloric acid after reaction, filtered,
Washed with the methanol solution containing 5% hydrochloric acid, then dry, pulverize again at 50 DEG C, obtain the nano combined material of montmorillonite/polyphenylene oxide
Material.Wherein, the mass ratio of montmorillonite and 2,6- xylenols is 1：1, the mass ratio of stannous chloride and 2,6- xylenols is
0.005：1, the mass ratio of dimethylamine and 2,6- xylenols is 0.005：1, the mol ratio of oxygen and 2,6- xylenols is
0.2：1.
Embodiment 2：
1st, the preparation of montmorillonite slurry：Montmorillonite powder is distributed in water and is configured to montmorillonite slurry, wherein montmorillonite
Mass ratio with water is 25：100；
2nd, the chemical modification of montmorillonite：It is stirred continuously down, Cetyltrimethylammonium bromide is added dropwise into montmorillonite slurry,
Wherein the mass ratio of Cetyltrimethylammonium bromide and montmorillonite is 0.4：1, reaction temperature is 100 DEG C, and the reaction time is
24h.Filtered after reaction, wash, in 120 DEG C of crushed after being dried, obtain modified montmorillonoid；
3rd, the preparation of modified montmorillonoid slurry：Modified montmorillonoid is distributed in toluene and is configured to modified montmorillonoid slurry,
Wherein the mass ratio of modified montmorillonoid and toluene is 0.25：1；
4th, the preparation of montmorillonite/polyphenylene oxide nano composite material：Cuprous iodide, pyridine are put into modified montmorillonoid slurry
In, it is stirred continuously, then 2,6- xylenols and ammonium persulfate is dissolved in toluene, and is added to the modification containing copper-amine complex
In montmorillonite slurry, 24h is reacted.Reaction solution is poured into precipitation of polyphenylene ether in the methanol solution containing 5% hydrochloric acid after reaction, filtered,
Washed with the methanol solution containing 5% hydrochloric acid, then dry, pulverize again at 120 DEG C, obtain the nano combined material of montmorillonite/polyphenylene oxide
Material.Wherein, the mass ratio of montmorillonite and 2,6- xylenols is 0.01：1, the mass ratio of cuprous iodide and 2,6- xylenols is
0.1：1, the mass ratio of pyridine and 2,6- xylenols is 0.1：1, the mol ratio of ammonium persulfate and 2,6- xylenols is 1：1.
Embodiment 3：
1st, the preparation of montmorillonite slurry：Montmorillonite powder is distributed in water and is configured to montmorillonite slurry, wherein montmorillonite
Mass ratio with water is 10：100；
2nd, the chemical modification of montmorillonite：It is stirred continuously down, KH560 is added dropwise into montmorillonite slurry, wherein KH560 is de- with covering
The mass ratio of soil is 0.1：1, reaction temperature is 80 DEG C, reaction time 6h.Filter, wash after reaction, powder after being dried at 100 DEG C
It is broken, obtain modified montmorillonoid；
3rd, the preparation of modified montmorillonoid slurry：Modified montmorillonoid is distributed in 1,4- dioxane to be configured to be modified to cover and taken off
The mass ratio of soil paste body, wherein modified montmorillonoid and Isosorbide-5-Nitrae-dioxane is 0.1：1；
4th, the preparation of montmorillonite/polyphenylene oxide nano composite material：Stannous chloride, n-butylamine are put into modified montmorillonoid slurry
In, it is stirred continuously, then 2,6- xylenols and hydrogen peroxide is dissolved in organic solvent, and is added to changing containing copper-amine complex
Property montmorillonite slurry in, react 8h.Reaction solution is poured into precipitation of polyphenylene ether in the methanol solution containing 5% hydrochloric acid after reaction, filtered,
Washed with the methanol solution containing 5% hydrochloric acid, then dry, pulverize again at 100 DEG C, obtain the nano combined material of montmorillonite/polyphenylene oxide
Material.Wherein, the mass ratio of montmorillonite and 2,6- xylenols is 0.08：1, the mass ratio of stannous chloride and 2,6- xylenols is
0.01：1, the mass ratio of n-butylamine and 2,6- xylenols is 0.01：1, the mol ratio of hydrogen peroxide and 2,6- xylenols is
0.5：1.
Embodiment 4：
1st, the preparation of montmorillonite slurry：Montmorillonite powder is distributed in water and is configured to montmorillonite slurry, wherein montmorillonite
Mass ratio with water is 10：100；
2nd, the chemical modification of montmorillonite：It is stirred continuously down, KH570 is added dropwise into montmorillonite slurry, wherein KH570 is de- with covering
The mass ratio of soil is 0.15：1, reaction temperature is 90 DEG C, reaction time 4h.Filter, wash after reaction, after 110 DEG C are dried
Crush, obtain modified montmorillonoid；
3rd, the preparation of modified montmorillonoid slurry：Modified montmorillonoid is distributed in 1,4- dioxane to be configured to be modified to cover and taken off
The mass ratio of soil paste body, wherein modified montmorillonoid and Isosorbide-5-Nitrae-dioxane is 0.15：1；
4th, the preparation of montmorillonite/polyphenylene oxide nano composite material：Stannous chloride, dimethylamine are put into modified montmorillonoid slurry
In, it is stirred continuously, then 2,6- xylenols and hydrogen peroxide is dissolved in organic solvent, and is added to changing containing copper-amine complex
Property montmorillonite slurry in, react 4h.Reaction solution is poured into precipitation of polyphenylene ether in the methanol solution containing 5% hydrochloric acid after reaction, filtered,
Washed with the methanol solution containing 5% hydrochloric acid, then dry, pulverize again at 110 DEG C, obtain the nano combined material of montmorillonite/polyphenylene oxide
Material.Wherein, the mass ratio of montmorillonite and 2,6- xylenols soil is 0.05：1, the mass ratio of stannous chloride and 2,6- xylenols
For 0.02：1, the mass ratio of n-butylamine and 2,6- xylenols is 0.02：1, the mol ratio of hydrogen peroxide and 2,6- xylenols is
0.6：1.Comparative example 1：In embodiment 3, step 2 is removed, i.e. montmorillonite is answered without modified synthesis montmorillonite/polyphenylene oxide nanometer
Condensation material.
Comparative example 2：In embodiment 3, remove step 1 and step 2, that is, synthesize polyphenyl ether material.
The performance test results of table 1
Claims (7)
1. the preparation method of a kind of montmorillonite/polyphenylene oxide nano composite material, it is characterised in that preparation method comprises the following steps：
(1) preparation of montmorillonite slurry：Montmorillonite powder is distributed in water and is configured to montmorillonite slurry, wherein montmorillonite and water
Mass ratio be 0.05~0.25：1；
(2) chemical modification of montmorillonite：It is stirred continuously down, modifying agent is added dropwise into montmorillonite slurry, wherein modifying agent is de- with covering
The mass ratio of soil is 0.05~0.4：1, reaction temperature is 40~100 DEG C, and the reaction time is 1~24h；Filter, wash after reaction,
In 60~120 DEG C of crushed after being dried, modified montmorillonoid is obtained；
(3) preparation of modified montmorillonoid slurry：Modified montmorillonoid is distributed in organic solvent and is configured to modified montmorillonoid slurry,
Wherein the mass ratio of modified montmorillonoid and organic solvent is 0.01~0.25：1；
(4) preparation of montmorillonite/polyphenylene oxide nano composite material：Cuprous halide, organic amine are put into modified montmorillonoid slurry,
It is stirred continuously, then 2,6- xylenols and oxidant is dissolved in organic solvent, is added to the modified illiteracy containing copper-amine complex
In de- soil paste body, 1~24h is reacted.Reaction solution is poured into precipitation of polyphenylene ether in the methanol solution containing 5% hydrochloric acid after reaction, filtered,
Washed with the methanol solution containing 5% hydrochloric acid, then dry, pulverize again at 50~120 DEG C, obtain montmorillonite/polyphenylene oxide nanometer and answer
Condensation material.
2. the preparation method of montmorillonite according to claim 1/polyphenylene oxide nano composite material, it is characterised in that modified
Agent is one kind in silane coupler, cationic surfactant.
3. the preparation method of montmorillonite according to claim 1/polyphenylene oxide nano composite material, it is characterised in that organic
Solvent is one kind in 1,4- dioxane, methanol, toluene, dimethylbenzene.
4. the preparation method of montmorillonite according to claim 1/polyphenylene oxide nano composite material, it is characterised in that halogenation
Cuprous one kind in stannous chloride, cuprous bromide, cuprous iodide.
5. the preparation method of montmorillonite according to claim 1/polyphenylene oxide nano composite material, it is characterised in that organic
Amine is one kind in dimethylamine, n-butylamine, pyridine, aniline.
6. the preparation method of montmorillonite according to claim 1/polyphenylene oxide nano composite material, it is characterised in that oxidation
Agent is one kind in oxygen, hydrogen peroxide, ammonium persulfate.
7. the preparation method of montmorillonite according to claim 1/polyphenylene oxide nano composite material, it is characterised in that 2,6- bis-
Cresols and the mass ratio of montmorillonite are 1~100：1, the mass ratio of cuprous halide and 2,6- xylenols is 0.005~0.1：
1, the mass ratio of organic amine and 2,6- xylenols is 0.005~0.1：1, the mol ratio of oxidant and 2,6- xylenols is
0.2~1：1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716798A (en) * | 2022-06-08 | 2022-07-08 | 河南源宏高分子新材料有限公司 | Environment-friendly flame-retardant transparent polyester material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951963A (en) * | 2014-05-12 | 2014-07-30 | 张国庆 | Method for preparing attapulgite/polyphenylether nanocomposite material |
-
2017
- 2017-11-15 CN CN201711129804.1A patent/CN107814925A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951963A (en) * | 2014-05-12 | 2014-07-30 | 张国庆 | Method for preparing attapulgite/polyphenylether nanocomposite material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716798A (en) * | 2022-06-08 | 2022-07-08 | 河南源宏高分子新材料有限公司 | Environment-friendly flame-retardant transparent polyester material and preparation method thereof |
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