CN1264719A - Process for preparing functional membrane material by modifying interface of powdered coal ash - Google Patents
Process for preparing functional membrane material by modifying interface of powdered coal ash Download PDFInfo
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- CN1264719A CN1264719A CN00105467A CN00105467A CN1264719A CN 1264719 A CN1264719 A CN 1264719A CN 00105467 A CN00105467 A CN 00105467A CN 00105467 A CN00105467 A CN 00105467A CN 1264719 A CN1264719 A CN 1264719A
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- water
- auxiliary agent
- flyash
- agent
- auxiliary
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
A process for preparing functional membrane material by modifying the interface of powdered coal ash as main raw material features that different assistants are used to modify the interface of powdered coal ash to activate its surface atoms for grafting with the functional groups in assistants, so obtaining the functional membranes with different functions. Said material has a superthin membrane structure on the interface of powdered coal ash, so it can be used as hydrophobic material, water-absorbing material, or functional filler used in production of rubber or plastics.
Description
The present invention relates to a kind of is the method that main raw material prepares functional membrane material with flyash, particularly flyash is carried out modifying interface, the fly ash grain surface atom is activated under certain conditions and then forms the method for functional membrane with functional functional group grafting in the different auxiliary agents by auxiliary agent.
It is the production technique of flyash hydrophobic powder that CN1054436A discloses the water-proof material that uses in a kind of building and the underground works, this technical scheme is to be body material with flyash, the silicone oil emulsion that organosilicon polymer or silicone oil material are formed by emulsifying agent emulsifications such as sapn or tweens is as auxiliary agent 1, the composite emulsion that forms as 2, two kinds of auxiliary agents of auxiliary agent with amine substance or enol class material polymkeric substance mixes flyash and forms cancellated hydrophobe through the effective constituent of reacting by heating and flyash.This hydrophobe has good water repellency, but the process for preparation of auxiliary agent is too complicated in this technical scheme, and produces to prescription by institute, the film function singleness that forms at the particle surface of flyash.
The object of the present invention is to provide a kind of by modifying interface of powdered coal ash being prepared the method for functional membrane material, can simplify with flyash by this method is the preparation that main raw material prepares auxiliary agent in the functional membrane material process, the material filming that obtains is good, and can have different characteristics because of the difference of grafting functional functional group.
The object of the present invention is achieved like this:
A kind of by modifying interface of powdered coal ash being prepared the method for functional membrane material, it is characterized in that this method comprises mixes auxiliary agent, water and flyash by a certain percentage, after the high-speed stirring, issues the produced film reaction at heating condition.Wherein, auxiliary agent is mainly by organosilicon polymer class material and be emulsified into emulsion with sapn, tween or both combinations as emulsifying agent and form, and the concrete prescription (by weight) of auxiliary agent comprises:
Organosilicon polymer class material 10～30%
Sapn, tween or both in conjunction with 5～10%
Water 60～80%
Above each component sum≤100%
Weight proportion between auxiliary agent, water and the flyash (meter by weight) is 1: 10～20: 20～40.
Preparation is during water-proof material, and silicone based material can be one or more the combination in one of poly-Union carbide A-162 and Methyl Hydrogen Polysiloxane Fluid or both and methyl-silicone oil, phenyl silicone oil, the hydroxy silicon oil in the above-mentioned auxiliary formula.
Preparation is during filler, and silicone based material can be one or more combination in vinyl ethyl ether base silane and Methyl Hydrogen Polysiloxane Fluid, methyl-silicone oil, phenyl silicone oil, the hydroxy silicon oil in the above-mentioned auxiliary formula.
The present invention is by preparing the method for functional membrane material to modifying interface of powdered coal ash, can also comprise that auxiliary agent do to modify monomer and add aqueous sodium hydroxide solution and initiator, linking agent, dispersion agent and emulsifying agent with the acrylic acid or the like material, the concrete prescription of auxiliary agent is:
Modify monomer 10～30%
NaOH: scale 3～10%
Initiator: persulphate (potassium or ammonium salt) 0.01～5%
Linking agent: epoxy chloropropane etc. 0.01～5%
Dispersion agent: hexanaphthene, dimethylbenzene etc. 0.01～20%
Emulsifying agent: sapn or tween 5～10%
Water 45～65%
Above each component sum=100%
In the case, the weight proportion of auxiliary agent, water, flyash is 1: 20～40: 60～80, and the material that obtains has water absorbing properties.
Be used as in the above-mentioned auxiliary formula modify monomeric acrylic acid or the like material can in vinylformic acid, methacrylic acid, the methyl methacrylate one or more.
The present invention has analysed in depth fine coal ash composition and structure on the basis of contrast patented technology, especially the structure of fly ash grain surface atom and activity detect and confirmed that interface of powdered coal ash (particle surface) has modifiable active atomic at certain condition.The present invention be exactly at the development of modifiable active atomic various can with the auxiliary agent of active atomic reaction in the interface of powdered coal ash, and definite reaction conditions.By active atomic grafting in functional group that has certain function in the auxiliary agent and the flyash (promptly modify), form functional membrane on the fly ash grain surface, the functional membrane material that makes flyash become to have certain function.Detected result shows that by this modifying method, at the formed functional membrane in fly ash grain surface, thickness is that hundreds of arrives in the scope of several thousand dusts, belongs to ultrathin membrane.These functional membrane materials are based on flyash, and active atomic in the surface and the effective constituent in the auxiliary agent are carried out Chemical bond to a certain degree, have formed the ultrathin membrane structure at interface of powdered coal ash.
In the preparation and testing process of ultrathin membrane, also found the variation of some regularity:
1. bigger change has taken place in the bound energy of elements such as the Si on flyash surface, Al, Ca, shows these
Element at the interface with auxiliary agent in some elements form coordinate bond grafting film forming;
2.Si, the bound energy of Al, Ca changes more greatly, the film that detects is thin more, prepared function material
The material effect is good more;
3. temperature variation, auxiliary agent variation all have considerable influence to thickness and film properties;
4. Mg all takes place at the membrane interface place in prepared functional materials
2+Enrichment phenomenon, and Mg
2+
Enriching quantity is many more, film is thin more, film properties is good more.
Research and detection have confirmed that interface of powdered coal ash has modifiability (being that its particle surface atom can be activated) under certain condition, can prepare the mould material that can be used as water-proof material, water-absorbing material and functional filler by flyash is carried out modifying interface on this basis.
The present invention can not only solve the pollution problem of flyash, for the CN1054436A patent, owing to no longer adopt enol class material to make auxiliary agent, make the process for preparation of auxiliary agent simplify greatly, be adjusted into a kind of auxiliary agent and auxiliary formula is optimized by two kinds of original auxiliary agents, reduced some inessential components.With different auxiliary agents flyash is carried out the functional membrane material that modifying interface can obtain having difference in functionality, these functional membrane materials can be used separately as water-proof material, water-absorbing material and functional filler according to itself characteristic.Functional membrane material is used in the production of products such as rubber, plastics as filler, make production cost of products such as rubber, plastics reduce greatly on the one hand, make on the other hand product mechanical property can be greatly improved, have favorable economic benefit and social benefit.
The present invention is described in further detail with embodiment below.
Flyash is the processing waste in fuel-burning power plant, is a kind of composition, and the chemical ingredients of the flyash of different sources has certain difference mutually with thing.The present invention has certain requirement to flyash, and flyash should have specific composition and thing mutually.Below the powdered coal ash that uses among each embodiment all satisfy following requirements.
The fly ash grain degree is not less than 80 orders, and main component and content thereof are:
SiO
2 ≥45％
Al
2O
3 25％～40％
CaO 3～12％
Fe
2O
3 5～15％
Above each component sum should≤100%
Wherein, the thing of Si, Al is Al mutually
6Si
2O
13, Al
2SiO
5Or Al
6Si
2O
13, Al
2SiO
5And SiO
2
Embodiment 1
The prescription of auxiliary agent is:
Poly-Union carbide A-162 24%
Methyl Hydrogen Polysiloxane Fluid 3%
Sapn 2%
Tween 5%
Glacial acetic acid 0.5%
Water 65.5%
Glacial acetic acid is a tensio-active agent in the prescription, with the weight of auxiliary agent as portion, after preparing, auxiliary agent adds 10 parts of water again, mix then in 20 parts the flyash, high-speed stirring (4000 rev/mins) 20 minutes, reaction is 5 hours under 150 ℃ condition, and the oven dry postcooling can obtain having the mould material of water repellency.
Embodiment 2
The prescription of auxiliary agent is:
Poly-Union carbide A-162 15%
Hydroxy silicon oil 5%
Sapn 5%
Tween 5%
Water 70%
As portion, add 20 parts of water with the weight of auxiliary agent after auxiliary agent prepares again, mix then in 40 parts the flyash, high-speed stirring (4000 rev/mins) 16 minutes, reaction is 4 hours under 180 ℃ condition, and the oven dry postcooling can obtain having the mould material of water repellency.
Embodiment 3
The prescription of auxiliary agent is:
Methyl Hydrogen Polysiloxane Fluid 15%
Hydroxy silicon oil 6%
Phenyl silicone oil 5%
Sapn 5%
Water 69%
As portion, add 15 parts of water with the weight of auxiliary agent after auxiliary agent prepares again, mix then in 40 parts the flyash, high-speed stirring (4000 rev/mins) 15 minutes, reaction is 4 hours under 200 ℃ condition, and the oven dry postcooling can obtain having the mould material of water repellency.
Embodiment 4
Poly-Union carbide A-162 10%
Phenyl silicone oil 8%
Methyl-silicone oil 7%
Sapn 6%
Glacial acetic acid 0.01%
Water 68.99%
As portion, add 10 parts of water with the weight of auxiliary agent after auxiliary agent prepares again, mix then in 40 parts the flyash, high-speed stirring (4000 rev/mins) 20 minutes, reaction is 4 hours under 120 ℃ condition, and the oven dry postcooling can obtain having the mould material of water repellency.
Embodiment 5
The prescription of auxiliary agent is:
Vinyl ethyl ether base silane 10%
Methyl Hydrogen Polysiloxane Fluid 4%
Hydroxy silicon oil 8%
Sapn 7%
Glacial acetic acid 0.3%
Water 70.7%
With the weight of auxiliary agent as portion, add 15 parts of water after auxiliary agent prepares again, mix in 40 parts the flyash high-speed stirring (4000 rev/mins) 18 minutes then, reaction is 4 hours under 280 ℃ condition, and the oven dry postcooling can obtain can be used as the functional membrane material of rubber or plastic filler.
Under the condition of high-speed stirring and heating, the ethoxy group splits away off from Siliciumatom, spills to be with certain active Si atom.This active Si atom can with the SiO of interface of powdered coal ash
2(the flyash main component is SiO to the bonding film forming
2And Al
2O
3), because Si, Al atom potential energy are bigger, have some coordinated water (H on every side
2O) or coordination OH exist, form the bridge of Si-O-Si, active pair of key vinyl of the other end band then easily plays addition reaction with double bond containing monomer, makes the carbochain lengthening, the carbochain group of this lengthening again with auxiliary agent in effective constituent connect chain, at the flyash surface filming.Embodiment 6 similarly.
Embodiment 6
The prescription of auxiliary agent is:
Vinyl ethyl ether base silane 5%
Phenyl silicone oil 3%
Methyl-silicone oil 6%
Sapn 8%
Glacial acetic acid 0.5%
Water 77.5%
With the weight of auxiliary agent as portion, add 15 parts of water after auxiliary agent prepares again, mix in 30 parts the flyash high-speed stirring (4000 rev/mins) 20 minutes then, reaction is 4.5 hours under 160 ℃ condition, and the oven dry postcooling can obtain can be used as the functional membrane material of rubber or plastic filler.
Embodiment 7
The prescription of auxiliary agent is:
Vinylformic acid 20%
NaOH (70% the aqueous solution) 10%
Potassium Persulphate 1.0%
Epoxy chloropropane 3%
Normal hexane 16%
Tween 5%
Water 45%
As portion, add 25 parts of water with the weight of auxiliary agent after auxiliary agent prepares again, mix in 60 parts the flyash, high-speed stirring (4000 rev/mins) 18 minutes, reaction is 4 hours under 50 ℃ temperature condition, and the oven dry postcooling can obtain having the mould material of water absorbing properties.
In this prescription, the acrylic acid or the like material is under the effect of NaOH and other auxiliary agent component, and with the active atomic grafting in the flyash, while self polymerization reaction take place generates the sodium polyacrylate film with strong absorptive.Embodiment 8 and embodiment 9 are similarly.
Embodiment 8
The prescription of auxiliary agent is:
Vinylformic acid 18%
Methyl methacrylate 8%
NaOH (93% the aqueous solution) 6%
Potassium Persulphate 1.7%
Ethylene glycol 0.8%
Hexanaphthene 10%
Sapn 7%
Water 48.5%
As portion, add 25 parts of water with the weight of auxiliary agent after auxiliary agent prepares again, mix then in 80 parts the flyash, high-speed stirring (4000 rev/mins) 12 minutes, reaction is 4 hours under 80 ℃ condition, and the oven dry postcooling can obtain having the mould material of water absorbing properties.
Embodiment 9
Vinylformic acid 10%
Methyl methacrylate 5%
NaOH (93% the aqueous solution) 5%
Ethylene glycol 0.5%
Hexanaphthene 8%
Sapn 9%
Water 62.5%
As portion, add 35 parts of water with the weight of auxiliary agent after auxiliary agent prepares again, mix in 70 parts the flyash, high-speed stirring (4000 rev/mins) 20 minutes, reaction is 4 hours under 70 ℃ condition, and the oven dry postcooling can obtain having the mould material of water absorbing properties.
Claims (9)
1. one kind by preparing the method for functional membrane material to modifying interface of powdered coal ash, it is characterized in that this method comprises mixes auxiliary agent, water and flyash by a certain percentage, after the high-speed stirring, issue the produced film reaction at heating condition, wherein, auxiliary agent is mainly by organosilicon polymer class material and be emulsified into emulsion with sapn, tween or both combinations as emulsifying agent and form, in the concrete prescription of auxiliary agent (by weight) comprising:
Organosilicon polymer class material 12～30%
Sapn, tween or both in conjunction with 5～10%
Water 60～80%
Above each component sum≤100%
Weight proportion between auxiliary agent, water and the flyash (meter by weight) is 1: 10～20: 20～40.
2. the method for claim 1 is characterized in that comprising that auxiliary agent does to modify monomer and add aqueous sodium hydroxide solution and initiator, linking agent, dispersion agent and emulsifying agent with the acrylic acid or the like material, and the concrete prescription of auxiliary agent comprises:
Modify monomer 10～30%
NaOH: scale 3～10%
Initiator: persulphate (potassium or ammonium salt) 0.01～5%
Linking agent: epoxy chloropropane etc. 0.01～5%
Dispersion agent: hexanaphthene or dimethylbenzene etc. 0.01～20%
Emulsifying agent: sapn or tween 5～10%
Water 45～65%
Above each component sum=100%
In the case, the weight proportion of auxiliary agent, water, flyash is 1: 20～40: 60～80, and the material that obtains has water absorbing properties.
3. the method for claim 1 is characterized in that preparing silicone based material in the auxiliary formula of water-proof material and can be one or more combination in one of poly-Union carbide A-162 and Methyl Hydrogen Polysiloxane Fluid or both and methyl-silicone oil, phenyl silicone oil, the hydroxy silicon oil.
4. the method for claim 1 is characterized in that preparing silicone based material in the auxiliary formula of functional stuffing and can be one or more combination in vinyl ethyl ether base silane and Methyl Hydrogen Polysiloxane Fluid, methyl-silicone oil, phenyl silicone oil, the hydroxy silicon oil.
5. method as claimed in claim 2, it is characterized in that preparing in the auxiliary formula of water-absorbing material as modify monomeric acrylic acid or the like material can in vinylformic acid, methacrylic acid, the methyl methacrylate one or more.
6. as claim 1 or the described method of claim 2, it is characterized in that flyash has specific composition and thing mutually, its granularity is not less than 80 orders, and wherein main component and content are:
SiO
2More than 45%
A1
2O
3 25％～40％
CaO 3～12％
Fe
2O
3 5～15％
Above each component sum≤100%
Wherein, the thing of Si, Al is Al mutually
6Si
2O
13, Al
2SiO
5Or Al
6Si
2O
13, Al
2SiO
5And SiO
2
7. method as claimed in claim 3, the temperature that it is characterized in that film formation reaction is 100～200 ℃.
8. method as claimed in claim 4, the temperature that it is characterized in that film formation reaction is 110～300 ℃.
9. method as claimed in claim 5, the temperature that it is characterized in that film formation reaction is 50～100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00105467A CN1117705C (en) | 2000-03-31 | 2000-03-31 | Process for preparing functional membrane material by modifying interface of powdered coal ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00105467A CN1117705C (en) | 2000-03-31 | 2000-03-31 | Process for preparing functional membrane material by modifying interface of powdered coal ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1264719A true CN1264719A (en) | 2000-08-30 |
| CN1117705C CN1117705C (en) | 2003-08-13 |
Family
ID=4577721
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00105467A Expired - Fee Related CN1117705C (en) | 2000-03-31 | 2000-03-31 | Process for preparing functional membrane material by modifying interface of powdered coal ash |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876464A (en) * | 2015-05-19 | 2015-09-02 | 河北工程大学 | Method for graft modification of fiber toughened fly ash |
| CN104891834A (en) * | 2015-05-19 | 2015-09-09 | 河北工程大学 | A grafting modification method of antibacterial anticorrosion fly ash |
| CN104891835A (en) * | 2015-05-19 | 2015-09-09 | 河北工程大学 | A graft modification method of flame-retardant fly ash |
| CN104961368A (en) * | 2015-06-18 | 2015-10-07 | 合肥工业大学 | Technically simple method for modifying fly ash |
| CN107268276A (en) * | 2017-07-14 | 2017-10-20 | 李占水 | A kind of waterproof alumina silicate Nomex and preparation method thereof |
-
2000
- 2000-03-31 CN CN00105467A patent/CN1117705C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876464A (en) * | 2015-05-19 | 2015-09-02 | 河北工程大学 | Method for graft modification of fiber toughened fly ash |
| CN104891834A (en) * | 2015-05-19 | 2015-09-09 | 河北工程大学 | A grafting modification method of antibacterial anticorrosion fly ash |
| CN104891835A (en) * | 2015-05-19 | 2015-09-09 | 河北工程大学 | A graft modification method of flame-retardant fly ash |
| CN104876464B (en) * | 2015-05-19 | 2017-12-08 | 河北工程大学 | A kind of graft-modification method of fiber reinforced flyash |
| CN104961368A (en) * | 2015-06-18 | 2015-10-07 | 合肥工业大学 | Technically simple method for modifying fly ash |
| CN107268276A (en) * | 2017-07-14 | 2017-10-20 | 李占水 | A kind of waterproof alumina silicate Nomex and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1117705C (en) | 2003-08-13 |
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