CN107715851B - Preparation method of high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material - Google Patents
Preparation method of high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract
The invention discloses a preparation method of a high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material, which comprises the steps of firstly acidifying iron oxide particles by hydrochloric acid, then adding a mixed solution of water, ethanol and ammonia water, carrying out ball milling, then dropwise adding tetraethyl orthosilicate for reaction, keeping reaction conditions, adding dodecylamine for reaction, then sintering, adding polyvinylidene chloride powder into a mixed solution of gelatin and ethanol for dissolution, heating for reaction, adding white oil and toluene as pore-forming agents, carrying out mixing and hot pressing, and then removing the pore-forming agents from the product.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a preparation method of a high-adsorbability modified iron oxide composite microporous polyvinylidene chloride material.
Background
Polyvinylidene chloride resin is a high molecular material with high barrier property, and the barrier property of the polyvinylidene chloride resin is dozens of times or even hundreds of times of that of a common packaging material. It also has self-extinguishing property, oil resistance and smell-keeping property, and is excellent in moisture-proofing and mildew-proofing properties, in particular it has low-temp. heat-sealing and heat-shrinking properties, and is easy to print, so that it is one of the favoured plastics for modern packaging industry, and can be extensively used for packaging food, medicine, precision instruments and various military articles, and is known as "green" packaging material. In addition, the latex prepared by the resin has better flame retardance and cohesiveness, so the latex has wide application in building materials and fireproof coatings.
The carbon molecular sieve is a novel carbon material developed in the early seventies, is taken as an excellent adsorbent, is valued by people, is applied to industries such as stone sleeve chemical environmental management, mechanical heat treatment and the like, and particularly shows superiority in air separation nitrogen production of a pressure swing adsorption process. The carbon molecular sieve is called carbon black pellet or carbon porous pellet, and its chemical composition is carbonized polyvinylidene chloride, and is a nonpolar compound, and is used as supporter of gas chromatography. The raw materials for preparing the carbon molecular sieve are many and have wide sources. Theoretically, carbon molecular sieves with different pore sizes and distributions can be obtained from different initial materials through different preparation processes. Experiments show that the raw material with low ash yield, high carbon content and high volatile content is more suitable for preparing the high-performance carbon molecular sieve.
The porous material has a large specific surface area and a through pore passage, so that the porous material becomes a hotspot material in the fields of catalysis, electrochemistry, adsorption and the like, and the controllable preparation research of the porous material attracts the attention of many researchers. The synthesis methods adopted for preparing the porous material at present mainly comprise a template method and a template-free method.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a preparation method of a high-adsorbability modified iron oxide composite microporous polyvinylidene chloride material.
The invention is realized by the following technical scheme:
a preparation method of a high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material comprises the following steps:
(1) adding 5-10 parts by weight of ferric oxide into a proper amount of hydrochloric acid solution, soaking for 20-50 minutes, adsorbing by a magnet, taking out, cleaning, adding 15-25 parts by weight of water, 50-60 parts by weight of ethanol and 1-5 parts by weight of ammonia water, carrying out ball milling and mixing for 5-8 hours, adding 0.1-0.3 part by weight of tetraethyl orthosilicate, and stirring for 4-8 hours at room temperature under the protection of nitrogen for later use;
(2) adding 0.5-2 parts by weight of dodecylamine into the particles obtained in the step (1), uniformly stirring and mixing by magnetic force to form a clear transparent solution, performing ball milling for 6-10 hours, and sintering for later use;
(3) dispersing the substance obtained in the step (2) in 5-10 parts by weight of gelatin and 40-60 parts by weight of ethanol, adding 10-20 parts by weight of polyvinylidene chloride powder, stirring for dissolving, heating to 75-85 ℃, reacting for 12-16 hours, and standing for 18-24 hours at room temperature for later use;
(4) adding 2-5 parts by weight of white oil and 2-8 parts by weight of methyl isobutyl carbinol into the product obtained in the step (3), reacting for 12-24 hours at 70-100 ℃, mixing for 5-15 minutes by a double-roll open mill, calendering into a sheet-shaped composite material, hot-pressing for 5-20 minutes by a flat vulcanizing machine, extracting toluene and white oil, drying and bagging to obtain the high-adsorbability modified iron oxide composite microporous polyvinylidene chloride material.
In the step (2), the sintering is carried out in the air after the temperature is raised from 25 ℃ to 800 ℃, the temperature raising rate is 1-2.5 ℃/min, the heat preservation is carried out for 2-4 hours, and then the sintering is carried out along with the furnace cooling to the normal temperature.
The mixing condition of the two-roll open mill in the step (4) is that the temperature is 160-180 ℃, and the rotation speed ratio of the front roll to the rear roll is 1 (1-1.2).
The hot-pressing condition of the plate vulcanizing machine in the step (4) is that the temperature is 180-.
The toluene and white oil extracted in the step (4) are obtained by adding the product into 80-100 parts by weight of solvent oil, and reacting at 60-70 ℃ for 2-4 hours.
The invention has the advantages that:
the invention firstly uses hydrochloric acid to acidify iron oxide particles, then adds the mixed solution of water, ethanol and ammonia water to ball mill, then drops tetraethyl orthosilicate to react, then keeps the reaction condition, adds dodecylamine to react and then sinters, then re-disperses in the mixed solution of gelatin and ethanol, adds polyvinylidene chloride powder to dissolve, heats and reacts, adds white oil and toluene as pore-forming agent to mix and hot press, removes the pore-forming agent to the product, and obtains the product, the acidified ball milled iron oxide particles are under the action of ammonia water, tetraethyl orthosilicate coats the surface of the iron oxide particles by sol-gel process to form a silicon dioxide layer, the added dodecylamine is used as precipitator to deposit the iron oxide and then sinters to form porous iron oxide with the surface coated with the silicon dioxide layer, improves the hydrophobic effect and the adsorbability, adds polyvinylidene chloride to carry out copolymerization grafting, the modified iron oxide particles are well dispersed in polyvinylidene chloride, and a pore-foaming agent is added to enable the material to form a carbon molecular sieve microporous structure, so that metal ions can be stabilized and the adsorbability can be improved.
Detailed Description
A preparation method of a high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material comprises the following steps:
(1) adding 8 parts by weight of ferric oxide into a proper amount of hydrochloric acid solution, soaking for 35 minutes, adsorbing by a magnet, taking out, cleaning, adding 20 parts by weight of water, 55 parts by weight of ethanol and 2 parts by weight of ammonia water, carrying out ball milling and mixing for 6 hours, adding 0.2 part by weight of tetraethyl orthosilicate, and stirring at room temperature for 6 hours under the protection of nitrogen for later use;
(2) adding 1.2 parts by weight of dodecylamine into the particles obtained in the step (1), adding into the solution, magnetically stirring and uniformly mixing to form a clear transparent solution, performing ball milling for 8 hours, and sintering for later use;
(3) dispersing the product obtained in the step (2) in 8 parts by weight of gelatin and 50 parts by weight of ethanol, adding 15 parts by weight of polyvinylidene chloride powder, stirring and dissolving, then heating to 80 ℃ for reaction for 14 hours, and standing at room temperature for 20 hours for later use;
(4) and (3) adding 3 parts by weight of white oil and 5 parts by weight of methyl isobutyl carbinol into the product obtained in the step (3), reacting for 18 hours at 85 ℃, mixing for 10 minutes by using a double-roller open mill, calendering into a sheet-shaped composite material, carrying out hot pressing for 15 minutes by using a flat vulcanizing machine, extracting toluene and white oil, drying and bagging to obtain the high-adsorbability modified iron oxide composite microporous polyvinylidene chloride material.
In the step (2), the sintering is carried out in the air after the temperature is raised from 25 ℃ to 800 ℃, the temperature raising rate is 1.5 ℃/min, the heat is preserved for 3 hours, and then the sintering is carried out along with the furnace cooling to the normal temperature.
And (3) mixing the materials in the two-roll open mill in the step (4) under the condition that the temperature is 170 ℃, and the rotation speed ratio of front and rear rolls is 1: 1.1.
And (4) carrying out hot pressing on the plate vulcanizing machine under the conditions that the temperature is 190 ℃ and the pressure is 15 MPa.
The toluene and white oil extracted in the step (4) are obtained by adding the product into 90 parts by weight of solvent oil and reacting for 3 hours at 65 ℃.
Claims (5)
1. A preparation method of a high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material is characterized by comprising the following steps:
(1) adding 5-10 parts by weight of ferric oxide into a proper amount of hydrochloric acid solution, soaking for 20-50 minutes, adsorbing by a magnet, taking out, cleaning, adding 15-25 parts by weight of water, 50-60 parts by weight of ethanol and 1-5 parts by weight of ammonia water, carrying out ball milling and mixing for 5-8 hours, adding 0.1-0.3 part by weight of tetraethyl orthosilicate, and stirring for 4-8 hours at room temperature under the protection of nitrogen for later use;
(2) adding 0.5-2 parts by weight of dodecylamine into the particles obtained in the step (1), uniformly stirring and mixing by magnetic force to form a clear transparent solution, performing ball milling for 6-10 hours, and sintering for later use;
(3) dispersing the substance obtained in the step (2) in 5-10 parts by weight of gelatin and 40-60 parts by weight of ethanol, adding 10-20 parts by weight of polyvinylidene chloride powder, stirring for dissolving, heating to 75-85 ℃, reacting for 12-16 hours, and standing for 18-24 hours at room temperature for later use;
(4) adding 2-5 parts by weight of white oil and 2-8 parts by weight of methyl isobutyl carbinol into the product obtained in the step (3), reacting for 12-24 hours at 70-100 ℃, mixing for 5-15 minutes by a double-roll open mill, calendering into a sheet-shaped composite material, hot-pressing for 5-20 minutes by a flat vulcanizing machine, extracting toluene and white oil, drying and bagging to obtain the high-adsorbability modified iron oxide composite microporous polyvinylidene chloride material.
2. The method for preparing a high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material according to claim 1, wherein the sintering in the step (2) is carried out by heating from 25 ℃ to 800 ℃, heating at a rate of 1-2.5 ℃/min, keeping the temperature for 2-4 hours, sintering in air, and furnace-cooling to normal temperature.
3. The method for preparing the high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material according to claim 1, wherein the mixing conditions of the two-roll mill in the step (4) are 160-180 ℃, and the rotation speed ratio of the front roll to the rear roll is 1 (1-1.2).
4. The method for preparing a highly adsorptive modified iron oxide composite microporous polyvinylidene chloride material according to claim 1, wherein the hot pressing condition of the press vulcanizer in the step (4) is 180-200 ℃ and 10-20 MPa.
5. The method for preparing a high-adsorptivity modified iron oxide composite microporous polyvinylidene chloride material according to claim 1, wherein the step (4) of extracting toluene and white oil is that the product is added into 80-100 parts by weight of solvent oil and reacted for 2-4 hours at 60-70 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186762A (en) * | 2007-12-03 | 2008-05-28 | 南京大学 | Method for enwrapping ferric oxide by silicon dioxide |
| CN101306327A (en) * | 2008-07-08 | 2008-11-19 | 大连理工大学 | Spiral carbon membrane and preparation method thereof |
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- 2017-09-13 CN CN201710820495.6A patent/CN107715851B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186762A (en) * | 2007-12-03 | 2008-05-28 | 南京大学 | Method for enwrapping ferric oxide by silicon dioxide |
| CN101306327A (en) * | 2008-07-08 | 2008-11-19 | 大连理工大学 | Spiral carbon membrane and preparation method thereof |
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