CN102151496B - Method for preparing polyvinyl formal (PVF) micro-filtration membrane - Google Patents
Method for preparing polyvinyl formal (PVF) micro-filtration membrane Download PDFInfo
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Abstract
The invention discloses a method for preparing a polyvinyl formal (PVF) micro-filtration membrane with high porosity and random average aperture adjustability. The method comprises the following steps of: dissolving polyvinyl alcohol (PVA) into water, adding secondary alkyl sulfonate, stirring the solution uniformly with heating, and adding any one of sulfuric acid and phosphoric acid for catalyzing; adding any pore auxiliary agent with micro-scale average grain diameter such as sodium silicate, heating the solution to the temperature of between 50 and 60 DEG C with stirring, adding formaldehyde, and stirring the solution uniformly to obtain foamed porous mixture; and injecting the mixture into a cylindrical die or a flaky die, transferring the die into a water bath kettle or a temperature control device, heating the mixture to the temperature of between 80 and 95 DEG C, performing acetalization reaction for 2 to 4 hours, then taking out the solid in the die, putting the solid into aqueous solution of sodium hydroxide and phenyl dimethylamine, removing the residual substances in the solid, rinsing the solid by using clean water, and drying the solid in a drying oven to obtain the white macromolecular PVF micropore filtration membrane with random average aperture.
Description
One, technical field
The present invention relates to the preparation method of a kind of polyvinyl formal (PVF) micro-filtration membrane.
Two, background technology
At present, the insoluble problems such as there is porosity lower (generally at 70-80%) in micropore filtering film, cost is higher for masking raw material (such as polytetrafluoroethylene (PTFE), Kynoar), the contradiction of flow and precision and film pollution, such as: US19860939159 is a kind of multifunctional high-precision filter.This filter is by a water intaking valve 1, coarse filter 2, sewage blow-down valve 3, magnetic filter 4, pump 5,6, one outlet valves 7 of fine filter, a machine body 8, wherein, the magnetic filter core is mounted in 4 one kinds of polyphosphazene polymer PVFs of magnetic filter filter core fine filter and installs 6.Through the water intaking valve transmission, fluid is to filter by coarse filter, magnetic filter, and pump and pipeline coarse filter along the line, the liquid outlet valve that then flows out, whole filtration is finished, and the filter quality fluid can be guaranteed.200720078224 patents are a kind of Multifunctional high-accuracy filter.This machine is comprised of inlet valve 1, coarse filtration 2, blowoff valve 3, magnetic filter 4, pump 5, smart filter 6, outlet valve 7 and body 8, and wherein the magnetic filter core is contained in the magnetic filter 4; Macromolecule " PVF " filter core is contained in the smart filter 6.Fluid process inlet valve, is flowed out by outlet valve after coarse filtration, magnetic filter, pump, smart filter along pipeline, and a whole set of filtration is complete, can guarantee the filter quality of fluid.
200710050486 patents are the preparation method of a kind of polyvinyl formal (PVF) micro-filtration membrane and filter disc thereof, it is with polyvinyl alcohol, sodium sulfate of polyethenoxy ether of fatty alcohol, it is in 10～40% the ethanol water that alkylbenzene sodium sulphate and glycerine join respectively concentration, through heating, stir when cooling the temperature to again below 30 ℃, add respectively again 50% sulfuric acid and 37% formaldehyde, behind the mixing on horizontal conveying belt uniform coating and coating is peeled off at tail end, perhaps mixed solution is injected mould, after the question response product approval, the product of the coating under peeling off or moulding is immersed by sulfuric acid, formaldehyde, in the mixed liquor that sodium sulphate and water form, under 50～70 ℃ temperature, reacted 3～10 hours, take out product, through cleaning, be cut into filter disc after the oven dry.Micro-filtration membrane, filter disc that this invention macromolecular material is produced, its hydrophily, water-tolerant, the porosity, circulation are large, and efficient is high.The WO1986EP00058 patent is that a smoke filter is applied to automobile exhaust, control air inlet Diesel engine pipeline by following flogic system: the Diesel engine (1) of rotary speed (n), PVF cooking fume filter (2), and EGT compares respectively concrete lower limit.If all measured values surpass limits value and represent that this equipment provides a signal.01119854 is a kind for the treatment of technology of oil-containing seawater, particularly a kind of processing method that contains high-concentration gasoline, diesel oil ballast water.Oil carrier oil-containing ballast water is entered collecting-tank, carry out grid, just heavy, it is characterized by: through the aeration oil removal, remove out oil slick and oil emulsion through membrane filtration again, then enter the secondary air-floatation device, again through the secondary membrane filtration, then enter shell medium and PVF filter etc.Water outlet is as clear as crystal, oil-containing≤5mg/L.Filter medium and film filtering system that this invention is used have all adopted low-cost raw material, and the regeneration that can recoil is again invested littlely, and operating cost is low, and is easy and simple to handle.Technical process does not produce residue, non-secondary pollution.This invention is not only applicable to the processing of oil carrier ballasting oil-containing seawater, is applicable to the processing with the pollution of oils water of other every profession and trades yet.
Three, summary of the invention
Purpose of the present invention to disclose exactly a kind of porosity up to more than 90%, can regulate arbitrarily that average pore size, operation are forced down, flux is large especially, energy-saving efficiency is high, the liquid resistance is little, film pollutes little, tool memory function, the preparation method of lower-cost polyvinyl formal (PVF) micro-filtration membrane.Thoroughly solved the mutual conflicting problem of filtering accuracy and flow." PVF " [Polyvinyl Formal] (polyvinyl formal) is commonly called as vinylon, same terylene, polyamide fibre, acrylic, belongs to high molecular polymer." PVF " is in theoretical proposition of nineteen twenty-eight.Nineteen forty-two, product emerged, and the fifties, the whole world entered industrialization production, and " PVF " material tradition is used for reeling off raw silk from cocoons weave cotton cloth (publicly-owned technology), makees fishing net, work clothes, parachute etc.; Now with its modification, sending out the hole becomes macromolecule " PVF " micropore filtering film for filtering (be commonly called as netted hole technology of vinylon, belong to the core technology tricks of the trade).
The present invention is dissolved in the water polyvinyl alcohol (PVA), adds secondary alkyl sulfonate, in the situation of heating, stir rear adding sulfuric acid or hydrochloric acid or phosphoric acid any one, carry out catalysis.Adding average grain diameter is any one pore auxiliary agent such as sodium metasilicate of micron level again.Stirring is heated to 50 ℃～60 ℃, adds formaldehyde again and stirs, and makes the porous plastid mixture of foaming.This mixture is injected cylinder mould or sheet mould, move in water-bath or the attemperating unit and be warming up to 80 ℃～95 ℃, behind the aldolisation 2～4 hours, take out solid in the mould, insert again and remove residuals in the solid in NaOH, the benzene dimethylamine aqueous solution (ratio of NaOH and benzene dimethylamine and water is 1～3 part: 2～5 parts: 2000～5000 parts), use the clear water rinsing afterwards, place oven dry in the drying box, obtain any average pore size white macromolecule " PVF " micropore filtering film.This filter membrane hydrophily strong (be commonly called as hydrophilic membrane, and average pore size capable of regulating) resilience is good, and porosity is up to more than 90%, have memory function, chemical stability is good, and the back washing performance is good, shock-resistant, be adapted to various mediums, be specially adapted to filtered water and air.Preparation method's technical measures of polyvinyl formal (PVF) micro-filtration membrane are as follows, and wherein said raw material is all with the parts by weight explanation.With 70～90 parts of polyvinyl alcohol (PVA), 30～120 parts of secondary alkyl sulfonates, average grain diameter is 60～120 parts of the sodium metasilicate of micron level.Be dissolved in respectively in 800～1200 parts of water, adding successively heats in the reactor with agitator and thermometer, and catalysis is carried out in any one acid (60～120 parts) that stirs in rear adding sulfuric acid or hydrochloric acid or the phosphoric acid, then stir and be warming up to 40～60 ℃, add 50～150 parts in formaldehyde, make the porous plastid mixture after the foaming after stirring, this mixture is injected drum type brake or piece-shape type mould, move in water-bath or the attemperating unit and be warming up to 80～95 ℃.Behind the aldolisation 2～4 hours, take out solid in the mould, insert again and remove residual material in the solid in NaOH, the benzene dimethylamine aqueous solution, with the clear water rinsing after 6～12 hours, place drying box to dry, just obtain white polyethylene alcohol formal (PVF) micropore filtering film of any average pore size.This filter membrane can be used for various medium, this filter membrane hydrophily (is commonly called as hydrophilic membrane by force, and the average pore size capable of regulating) resilience is good, porosity is up to more than 90%, the tool memory function, and chemical stability is good, the back washing performance is good, shock-resistant, be adapted to various mediums, be specially adapted to filtered water and air.Pore auxiliary agent sodium metasilicate average grain diameter is 0.1～9 micron; Curing agent is benzene dimethylamine; Operation is pressed and is 0.01MPa.
Secondary alkyl sulfonate is light yellow liquid or solid, has good detergency, spumescence, emulsifying ability and wetting power etc.All very stable in wider pH value scope, resistance to oxidation is also very strong, and is little to skin irritatin, nontoxic, and biological degradability is better than sodium n-alkylbenzenesulfonate (LAS).By n-alkane and sulfur dioxide and oxygen reaction, make through neutralization again.
Benzene dimethylamine claims again m-xylene diamine, meta-xylene methylamine, as main component take m-xylene diamine. contain a certain amount of p dimethylamine's mixture, colourless or little yellow transparent liquid, molecular weight 136.2, relative density (20 ℃/4 ℃) 1.051,14.1 ℃ at freezing point. 248 ℃ of boiling points, 143 ℃ of flash-points, refractive index 1.5790, viscosity (20 ℃) 6.8mPas.Water-soluble, methyl alcohol, ethanol, butanols, acetone, butanone, chloroform, benzene,toluene,xylene, pyridine, ether, ethyl acetate are insoluble in benzinum, n-hexane, cyclohexane.Low toxicity, LD501750mg/kg stimulates eyes and skin.As the cold curing agent of epoxy resin, can be regarded as the aliphatic polyamine that contains aromatic rings, be bordering on aromatic amine on the structure, on the performance again near aliphatic polyamine.With reference to consumption 16～19phr, working life 20min.Condition of cure rT/ (2～6h), do not produce toxicity smog, excitant and toxicity are all little, and heat resistance is higher than aliphatic polyamine, 130～150 ℃ of heat distortion temperatures.
Four, specific embodiment
Polyvinyl alcohol (PVA) is dissolved in the water, adds secondary alkyl sulfonate, in the situation of heating, stir rear adding sulfuric acid or hydrochloric acid or phosphoric acid any one, carry out catalysis.Adding average grain diameter is the sodium metasilicate pore auxiliary agent of micron level again.Stirring is heated 55 ℃～60 ℃, adds formaldehyde again and stirs, and makes the porous plastid mixture of foaming.This mixture is injected cylinder mould or sheet mould, move in water-bath or the attemperating unit and be warming up to 85 ℃～95 ℃, behind the aldolisation 3～4 hours, take out solid in the mould, insert again in the sodium hydrate aqueous solution, remove residuals in the solid, use the clear water rinsing afterwards, place oven dry in the drying box, obtain any average pore size white macromolecule " PVF " micropore filtering film.Wherein said raw material is all with the parts by weight explanation.With 80～90 parts of polyethylene (PVA), 40～110 parts of secondary alkyl sulfonates, average grain diameter is 70～110 parts of the sodium metasilicate pore auxiliary agents of micron level.Be dissolved in respectively in 900～1200 parts of water, adding successively heats in the reactor with agitator and thermometer, and catalysis is carried out in any one acid (70～120 parts) that stirs in rear adding sulfuric acid or hydrochloric acid or the phosphoric acid, then stir and be warming up to 50～60 ℃, add 60～140 parts in formaldehyde, make the porous plastid mixture after the foaming after stirring, this mixture is injected drum type brake or piece-shape type mould, move in water-bath or the attemperating unit and be warming up to 60～90 ℃.Behind the aldolisation 3～4 hours, take out solid in the mould, insert again and remove residual material in the solid in NaOH, the benzene dimethylamine aqueous solution (ratio of NaOH and benzene dimethylamine and water is 1～3 part: 2～5 parts: 2000～5000 parts), with the clear water rinsing after 6～12 hours, place drying box to dry, just obtain white polyethylene alcohol formal (PVF) micropore filtering film of any average pore size.Pore auxiliary agent sodium metasilicate average grain diameter is 0.1～9 micron; Thereby carry out membrane aperture by the pore auxiliary agent that adds different micron levels and regulate the film that obtains different average pore diameters; Curing agent is benzene dimethylamine.Operation is pressed and is 0.01MPa.
Claims (2)
1. the preparation method of polyvinyl formal PVF micro-filtration membrane is characterized in that:
Wherein, raw material is all with parts by weight, with 70～90 parts of PVAC polyvinylalcohols, and 30～120 parts of secondary alkyl sulfonates, average grain diameter is 60～120 parts of the sodium metasilicate pore auxiliary agents of micron level; Be dissolved in respectively in 800～1200 parts of water, adding successively heats in the reactor with agitator and thermometer, and catalysis is carried out in stir in rear adding sulfuric acid or hydrochloric acid or the phosphoric acid 60～120 parts of any one acid, then stir and be warming up to 40～60 ℃, add 50～150 parts in formaldehyde, make the porous plastid mixture after the foaming after stirring, this mixture is injected drum type brake or piece-shape type mould, move in the water-bath and be warming up to 80～95 ℃; Behind the aldolisation 2～4 hours, take out solid in the mould, insert again and remove residual material in the solid in NaOH, the benzene dimethylamine aqueous solution, use the clear water rinsing after 6～12 hours, place drying box to dry, just obtain the white polyethylene alcohol formal PVF micro-filtration membrane of any average pore size; Carry out membrane aperture by the pore auxiliary agent that adds different micron levels and regulate, thus the film of acquisition different average pore diameters; Curing agent is benzene dimethylamine; Operation is pressed and is 0.01Mpa;
Pore auxiliary agent sodium metasilicate powder average grain diameter is 0.1～9 micron.
2. the preparation method of a kind of polyvinyl formal PVF micro-filtration membrane according to claim 1, it is characterized in that: in NaOH, the benzene dimethylamine aqueous solution, the ratio of NaOH and benzene dimethylamine and water is 1～3 part: 2～5 parts: 2000～5000 parts.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102614787A (en) * | 2012-03-29 | 2012-08-01 | 南昌大学 | Method for preparing hydrophilic macromolecule microporous composite membrane |
| CN102921312B (en) * | 2012-11-01 | 2014-08-20 | 北京市射线应用研究中心 | Polyvinyl formal filtering membrane and preparation method thereof |
| CN104327201B (en) * | 2014-11-21 | 2018-05-04 | 中国农业科学院农业资源与农业区划研究所 | A kind of polyvinyl formal applied to negative pressure seepage controllor |
| CN106512759A (en) * | 2016-12-06 | 2017-03-22 | 周潇潇 | Macromolecule filter membrane material |
| CN108031310A (en) * | 2017-12-13 | 2018-05-15 | 四川银趣环保科技有限公司 | A kind of preparation method of the filtering net film based on graphene and high molecular material |
| CN108031191A (en) * | 2017-12-23 | 2018-05-15 | 刘顶康 | A kind of preparation method of polyvinyl formal filter membrane |
| CN110624416A (en) * | 2019-08-26 | 2019-12-31 | 陈志华 | Production method of polyvinyl propionaldehyde microfiltration filter material |
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| US6146747A (en) * | 1997-01-22 | 2000-11-14 | Usf Filtration And Separations Group Inc. | Highly porous polyvinylidene difluoride membranes |
| CN101041721A (en) * | 2006-03-24 | 2007-09-26 | 比亚迪股份有限公司 | Vacuum flow-casting film forming machine and method for preparing composite proton interchange membrane |
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| JP3673452B2 (en) * | 2000-07-03 | 2005-07-20 | 株式会社荏原製作所 | Pollution-resistant porous filtration membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6146747A (en) * | 1997-01-22 | 2000-11-14 | Usf Filtration And Separations Group Inc. | Highly porous polyvinylidene difluoride membranes |
| CN101041721A (en) * | 2006-03-24 | 2007-09-26 | 比亚迪股份有限公司 | Vacuum flow-casting film forming machine and method for preparing composite proton interchange membrane |
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Effective date of registration: 20191225 Address after: 610000 room 1, floor 3, building 4, No. 55, huanjin Road, Qingyang District, Chengdu City, Sichuan Province Patentee after: Sichuan Haoxin Quantum Technology Co., Ltd Address before: 610300, No. 32 Datong new street, Datong Town, Qingbaijiang District, Sichuan, Chengdu Patentee before: Chengdu Qingbaijiang Fufamo Filter Device Co., Ltd. |
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