CN100537644C - Method for preparing inorganic matter micropowder hybrid polyvinylidene fluoride - Google Patents
Method for preparing inorganic matter micropowder hybrid polyvinylidene fluoride Download PDFInfo
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- CN100537644C CN100537644C CNB2007100597811A CN200710059781A CN100537644C CN 100537644 C CN100537644 C CN 100537644C CN B2007100597811 A CNB2007100597811 A CN B2007100597811A CN 200710059781 A CN200710059781 A CN 200710059781A CN 100537644 C CN100537644 C CN 100537644C
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Abstract
The present invention relates to a preparation method of an inorganic micro-powder hybrid polyvinylidene fluoride membrane, and the technology is that: (1) the preparation of casting solution, the polyvinylidene fluoride powder and the inorganic micro-power with the volume ratio of polyvinylidene fluoride powder/inorganic micro-power of 1 to 3/ 3 to 1 are added into the dimethylacetamide solvent with the volume of 8 to 10 times of the polyvinylidene fluoride powder, then the complete stirring are carried out at 78 to 82 DEG C till the polyvinylidene fluoride powder is dissolved completely, so as to get the clarified casting solution; the inorganic micro-powder is calcium carbonate, the particle size is 60 to 90 nm or 0.8 to 1.6 Mum; (2) the static defoaming: the casting solution which is obtained in (1) is carried out the constant temperature static defoaming for 2 to 3 hours at 78 to 82 DEG C; (3) the membrane preparation: the casting solution after the defoaming is scraped into a flat membrane with the thickness of 100 to 150 Mum on a glass plate; then the obtained membrane is immersed in the ultrafiltration water coagulation bath with the constant temperature of 10 to 60 DEG C for forming, and the inorganic micro-powder hybrid polyvinylidene fluoride membrane can be obtained after the automatic shedding of the membrane.
Description
Technical field
The present invention relates to a kind of membrane preparation technology, be specially a kind of preparation method who is intended to improve the inorganic matter micropowder hybrid polyvinylidene fluoride of polyvinylidene difluoride (PVDF) film properties.International Patent classificating number intends being Int.Cl C02F1/40 (2006.01).
Background technology
The research and development of inorganic in recent years-organic hybrid films become one of focus of film research.The characteristics of inorganic-organic hybrid films are: it is comprehensive organic membrane and mineral membrane advantage separately not only, remedies their defective, and can develop the over-all properties that single mould material did not originally have, and satisfies specific needs.At present, along with the development of nanotechnology and nano material, many researchs begin to utilize inorganic nano material to prepare nano inorganic-organic composite filtering film again.For example:
Chinese patent literature CN1724586A discloses a kind of nanometer aluminium oxide modified polyvinilidene fluoride separatory membrane and preparation method thereof.Modified membrane has kept the original excellent characteristic of polyvinylidene fluoride separation membrane, has strengthened the wetting ability of film, has improved the resistance to crocking of film, makes the effluent flux of film be greatly enhanced; But the modified membrane rejection of this kind method preparation is lower.
Chinese patent literature CN1579602A discloses a kind of sintering α-aluminum oxide to the unsymmetric structure/preparation method of polyvinylidene blending hollow-fibre membrane, the prescription of special-purpose preparation liquid and goods thereof.This method is raw material with the polyvinylidene difluoride (PVDF), disperses sintering α-aluminum oxide in the good solvent the inside of polyvinylidene difluoride (PVDF) earlier, makes it to produce reaction with the polyvinylidene difluoride (PVDF) that adds, and forms mixed solution; Add hydrophilic compounds then in mixed solution, this hydrophilic compounds and above-mentioned mixed solution react, and obtain the preparation liquid of certain viscosity.This preparation liquid is prepared hollow-fibre membrane by phase inversion process.Therefore, it is reasonable that this invention has the composition and the ratio thereof of preparation liquid prescription, film-forming process is comparatively simple, lower to technology, equipment requirements, the performance complement of various components, synergy adopts common process just directly can spin out characteristics such as larger aperture, high permeation flux and the asymmetric polyvinylidene difluoride (PVDF) tubular fibre of pore size distribution porous-film.But the polyvinylidene difluoride (PVDF) hollow-fibre membrane of this method preparation is because the aperture is bigger, and same rejection is lower, and actual application value is little.
People such as beam Groceries (beam Groceries etc. nanometer γ-Al
2O
3The structural research of/PVDF hollow-fibre membrane. water technology, 2004.08.30 (4): 199～201) by in the polyvinylidene difluoride (PVDF) film-casting liquid, adding inorganic nano Al
2O
3Particle adopts dry-wet spinning to prepare γ-Al
2O
3Hollow-fibre membrane, permeability energy, separation performance and the mechanical property of film all have some improvement.Porosity is when improving, and its maximum diameter of hole is corresponding to diminish, and the rejection of bovine serum albumin is brought up to 67.20% from 25.11%.Though the rejection of film increases, the film rejection of this method preparation is still not high, and the practical application meaning is also little.
People such as Peng Yuelian (Peng Yuelian etc. nanometer SiO
2Influence research to polyvinylidene fluoride (PVDF) ultrafiltration membrane. membrane science and technology, 2006,02,26 (1): 31～34) by in the polyvinylidene difluoride (PVDF) film-casting liquid, adding nano inoganic particle SiO
2Make nano inorganic-organic hybrid films, added proper amount of nano SiO
2Though the water flux of film can increase, and rejection can not reduce, and it is high and not obvious that its water flux is carried, and only improved 1.1 times, and actual application value is little.
K.Ebert. wait the people " mineral filler is to the influence of apertured polymeric film compacting behavior " (referring to membrane science, 2004,233:71-78; K.Ebert, D.Fritsh, J.koll et al.Influence ofinorganic fillers on the compaction behaviour of porous polymer basedmembranes.J Membr Sci.2004,233:71-78) in the literary composition polymer P VDF and LiCl Additive are dissolved in the solvent, add nano-TiO then
2Particle is made into the homogeneous film-casting liquid, adopts inversion of phases to make hybridized film, is coagulation bath with water, and is dissolved in PVDF and LiCl and is made into film-casting liquid in the solvent and is equipped with pvdf membrane to make.Coating one deck is selected layer PVA/CD on two kinds of films respectively, makes it to heat 1h and carry out heat cross-linking in 180 ℃ of baking ovens, forms composite membrane.Discover, under 30bar operation pressure, PVDF-TiO
2Hybridized film is compared with pvdf membrane and is not easy densification, under higher working pressure and temperature, demonstrates mechanical stability preferably.To with pvdf membrane or PVDF-TiO
2The infiltration evaporation process that hybridized film has been carried out ethanol dehydration for the hydrophilic composite film that supports, operating temperature range is that 78 ℃ (1bar) are to 135 ℃ (6.5bar), discover in operating temperature range, with organic-inorganic hybridized porous-film is the hydrophilic film of support, also demonstrates penetrating quality preferably when higher flux is arranged even at 135 ℃.This method complicated process of preparation is unfavorable for suitability for industrialized production.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is, a kind of preparation method of inorganic matter micropowder hybrid polyvinylidene fluoride is provided, and it is simple that this preparation method has a film-forming process, and is low to technology, equipment requirements, is suitable for industrial characteristics; When the water flux of gained film product was improved by a relatively large margin, the rejection of film also increased.
The technical scheme that the present invention solve the technical problem is: design a kind of preparation method of inorganic matter micropowder hybrid polyvinylidene fluoride, this preparation method adopts following technology:
(1) preparation film-casting liquid: be 1～3/3～1 polyvinylidene difluoride (PVDF) powder and inorganic matter micropowder with polyvinylidene difluoride (PVDF) powder/inorganic matter micropowder volume ratio, also has the additives polyethylene glycol powder, the molecular weight of described polyoxyethylene glycol powder is 600～20000, add-on is 0.5～1.5 times of polyvinylidene difluoride (PVDF) powder volume content, join in the solvent of 8～10 times of polyvinylidene difluoride (PVDF) powder volume, stir down fully at 78-82 ℃, dissolve fully to the polyvinylidene difluoride (PVDF) powder, obtain clarifying film-casting liquid; Described inorganic matter micropowder is a lime carbonate, and its particle diameter is 60～90nm or 0.8～1.6 μ m; Described solvent is a N,N-DIMETHYLACETAMIDE;
(2) standing and defoaming: with the film-casting liquid of (1) gained under 78～82 ℃, constant temperature standing and defoaming 2～3 hours;
(3) system film: the film-casting liquid that deaeration is finished is scraped on sheet glass and is made the flat sheet membrane that thickness is about 100～150 μ m; Again the film of gained is immersed in steady temperature and is in 10～60 ℃ the ultrafiltration water precipitation bath, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain described inorganic matter micropowder hybrid polyvinylidene fluoride.
Compared with the prior art, preparation method's of the present invention advantage is that film-forming process is simple, and is low to technology, equipment requirements, is suitable for the industrialization actual production.The present invention designs the nanometer～submicron order inorganic matter micropowder of adding, the water flux of film is improved by a relatively large margin, simultaneously the rejection of film also increases, and described inorganic matter micropowder suitability for industrialized production, and the industrializing implementation that is easy to inorganic matter micropowder hybrid polyvinylidene fluoride is promoted.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment.
A kind of inorganic matter micropowder hybrid polyvinylidene fluoride preparation method (hereinafter to be referred as the preparation method) of the present invention's design, its technology is as follows:
(1) preparation film-casting liquid: be 1～3/3～1 polyvinylidene difluoride (PVDF) powder and inorganic matter micropowder with polyvinylidene difluoride (PVDF) powder/inorganic matter micropowder volume ratio, join in the solvent of 8～10 times of polyvinylidene difluoride (PVDF) powder volume, fully stir down at 78-82 ℃, dissolve fully to the polyvinylidene difluoride (PVDF) powder, obtain clarifying film-casting liquid; Described inorganic matter micropowder is a lime carbonate, and particle diameter is 60～90nm or 0.8～1.6 μ m; Described solvent is a N,N-DIMETHYLACETAMIDE.Described polyvinylidene difluoride (PVDF)/inorganic matter micropowder volume ratio embodiment specific design is 1/3,1/2,1,3/2,2,3; The particle diameter of described inorganic matter micropowder lime carbonate is except that described 60～90nm and 0.8～1.6 mu m range, and the present invention has also inquired into the influence of the inorganic matter micropowder of other particle diameters to the polyvinylidene difluoride (PVDF) membrane flux.Test shows, though other particle size range also feasible in varying degrees, it is satisfactory for result all to be not so good as described particle size range.
(2) standing and defoaming: with the film-casting liquid of above-mentioned (1) gained under 78～82 ℃, constant temperature standing and defoaming 2～3 hours;
(3) system film: the film-casting liquid that deaeration is finished is scraped on sheet glass and is made the flat sheet membrane that thickness is about 100～150 μ m; It is in 10～60 ℃ the ultrafiltration water precipitation bath that the film of gained is immersed in steady temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain described inorganic matter micropowder hybrid polyvinylidene fluoride.
Preparation method's of the present invention further feature is, in described inorganic matter micropowder, and preferred nano level inorganic matter micropowder, concrete particle diameter is 60～90nm.
Preparation method's of the present invention further feature is, will be in described preparation preparation liquid technology, and add simultaneously with described polyvinylidene difluoride (PVDF) powder, inorganic matter micropowder and to also have the additives polyethylene glycol powder in the solvent N,N-DIMETHYLACETAMIDE.The molecular weight of described polyoxyethylene glycol powder is 600～20000, and embodiment has adopted 600,1000,6000 and 20000 molecular weight, and its add-on is 0.5～1.5 times of polyvinylidene difluoride (PVDF) powder volume content, embodiment has specifically adopted 0.5 times, 1 times and 1.5 times.The additives polyethylene glycol powder is a water-soluble polymers, joins mainly to play effects such as dispersion, thickening in the film-casting liquid; When film-casting liquid contact precipitation bath, can be separated, polyoxyethylene glycol mainly is enriched in the dilute phase, can cause the formation in duct, is good polymer pore former.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below, but embodiment does not limit the present invention.
Embodiment 1
12g micron order inorganic matter micropowder and 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml solvent N,N-DIMETHYLACETAMIDE, fully stir down, dissolve fully, obtain clarifying film-casting liquid until polyvinylidene difluoride (PVDF) at 78 ℃.Under 80 ℃, several 3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrape and make the flat sheet membrane that thickness is about 100 μ m, (precipitation bath used herein is through the filtering ultrafiltration water of the hollow-fibre membrane of this specification to put into 20 ℃ of ultrafiltration water of constant temperature, membrane pore size is between 20-1000A °, down together), solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 2
9g micron order inorganic matter micropowder and 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 80 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF), obtain film-casting liquid.Under 82 ℃, several 2 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 120 μ m, put into 20 ℃ of described ultrafiltration water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 3
6g micron order inorganic matter micropowder and 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 82 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF), obtain film-casting liquid.Under 82 ℃, several 2 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 150 μ m, put into 20 ℃ of described ultrafiltration water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 4
4g micron order inorganic matter micropowder and 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 78 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF), obtain film-casting liquid.Under 78 ℃, several 3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 150 μ m, put into 20 ℃ of described ultrafiltration water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 5
3g micron order inorganic matter micropowder and 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 80 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF), obtain film-casting liquid.Under 80 ℃, several 2.5 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 100 μ m, put into 20 ℃ of described ultrafiltration water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 6
18g micron order inorganic matter micropowder and 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 82 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF), obtain film-casting liquid.Under 80 ℃, several 2 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 130 μ m, put into 20 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 7
6g micron order inorganic matter micropowder and 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 78 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF), obtain film-casting liquid.Under 80 ℃, several 2.5 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 140 μ m, put into 10 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 8
18g micron order inorganic matter micropowder, 21.4g polyvinylidene difluoride (PVDF) and 7.3g additives polyethylene glycol (molecular weight 20000) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 78 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 80 ℃, several 3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 100 μ m, put into 10 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 9
2g micron order inorganic matter micropowder, 21.4g polyvinylidene difluoride (PVDF) and 21.9g polyoxyethylene glycol (molecular weight 20000) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 78 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 80 ℃, several 2～3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 120 μ m, put into 10 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 10
2g micron order inorganic matter micropowder, 21.4g polyvinylidene difluoride (PVDF) and 14.5g polyoxyethylene glycol (molecular weight 10000) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 80 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 80 ℃, several 2.5 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 100 μ m, put into 60 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 11
18g micron order inorganic matter micropowder and 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 78 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF), obtain film-casting liquid.Under 80 ℃, several 3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 150 μ m, put into 60 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 12
6g micron order inorganic matter micropowder, 21.4g polyvinylidene difluoride (PVDF) and 7.2g additives polyethylene glycol (molecular weight 600) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 80 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 80 ℃, several 2～3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 100 μ m, put into 60 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 13
5g nano-grade inorganics micro mist, 21.4g polyvinylidene difluoride (PVDF) and 21.8g polyoxyethylene glycol (molecular weight 10000) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 78 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 82 ℃, several 2 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 130 μ m, put into 10 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 14
15g nano-grade inorganics micro mist, 21.4g polyvinylidene difluoride (PVDF) and 14.4g polyoxyethylene glycol (molecular weight 600) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 80 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 80 ℃, several 2～3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 100 μ m, put into 0 ℃ of water of 1 constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 15
1.7g nano-grade inorganics micro mist, 21.4g polyvinylidene difluoride (PVDF) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 80 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF), obtain film-casting liquid.Under 78 ℃, several 2.5 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 150 μ m, put into 10 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 16
1.7g nano-grade inorganics micro mist, 21.4g polyvinylidene difluoride (PVDF) and 7.3g polyoxyethylene glycol (molecular weight 6000) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 78 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 80 ℃, several 3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 120 μ m, put into 60 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 17
15g nano-grade inorganics micro mist, 21.4g polyvinylidene difluoride (PVDF) and 21.8g polyoxyethylene glycol (molecular weight 6000) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 78 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 80 ℃, several 3 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 140 μ m, put into 60 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
Embodiment 18
5g nano-grade inorganics micro mist, 21.4g polyvinylidene difluoride (PVDF) and 14.6g polyoxyethylene glycol (molecular weight 20000) are mixed in the 108ml N,N-DIMETHYLACETAMIDE, and 80 ℃ of following stirring and dissolving are dissolved fully to polyvinylidene difluoride (PVDF) and polyoxyethylene glycol, obtain film-casting liquid.Under 80 ℃, several 2.5 hours of constant temperature standing and defoaming.Film-casting liquid is poured on the sheet glass, scrapes and make the flat sheet membrane that thickness is about 100 μ m, put into 60 ℃ of water of constant temperature, solidification forming, treat that film comes off from the sheet glass automatically after, obtain inorganic matter micropowder hybrid polyvinylidene fluoride.
The present invention has carried out the actual test of water flux to embodiment 1-18 prepared inorganic matter micropowder (nanometer～submicron) hydridization polyvinylidene difluoride (PVDF) (flat board) films, and test result is listed in the table 1.Water flux in the table 1 calculates can be according to following formula (a); The calculating of rejection can be according to following formula (b).In table 1, embodiment is numbered 19 the comparative example that is, does not promptly add the polyvinylidene fluoride film of described inorganic matter micropowder or inorganic matter micropowder and polyoxyethylene glycol, and its processing condition are same as embodiment 1.
The formula of described calculating membrane flux (a) is:
Jw＝V/At(a)
In the formula (a): Jw----pure water flux (L/m
2H);
V-----sees through liquid long-pending (L);
Useful area (the m of A-----film
2);
T-----obtains the V volume and sees through the required time (h) of liquid.
The concentration of utilizing ultraviolet spectrophotometer to measure ovalbumin stoste and filtrate also is designated as C respectively
1And C
2The rejection of described tested film can be calculated by following formula (b):
In the formula (b): the rejection of the tested film of R------;
C
1The concentration of-----stoste;
C
2The concentration of-----filtrate.
By table 1 measured data as can be seen, inorganic matter micropowder (nanometer～submicron) hybrid polyvinylidene fluoride through the inventive method preparation, it is fairly obvious that water flux improves effect: only adding inorganic matter micropowder, when not adding additives polyethylene glycol, water flux can improve 3.8～13.6 times (referring to embodiment 1-6,19), rejection has improved 2.1～2.5 times (referring to embodiment 1-6,19).Because in actual production, need to add additives polyethylene glycol, the inventive method also adds additives polyethylene glycol when adding described inorganic matter micropowder after, its water flux can improve about 11～1000 times (referring to embodiment 8-10,12-14,16-18,19), rejection also can improve about 1.9～2.6 times (referring to embodiment 8-10,12-14,16-18,19), water flux and rejection still remain in the reasonable range, are fit to industrial practical application.
Prepared membrane flux of table 1 embodiment and rejection testing data table
Based on the foregoing description, the desirable processing condition that the present invention prepares inorganic matter micropowder hybrid polyvinylidene fluoride are designed to: the molecular weight of described additives polyethylene glycol powder is 10000, and add-on is 1.5 times of polyvinylidene difluoride (PVDF) powder volume content; The particle diameter of described inorganic matter micropowder is 60～90nm, and the volume ratio of itself and polyvinylidene difluoride (PVDF) powder is 1/1; Described coagulation bath temperature is 10 ℃.
Claims (3)
1. the preparation method of an inorganic matter micropowder hybrid polyvinylidene fluoride, its technology is as follows:
(1) preparation film-casting liquid: be 1～3/3～1 polyvinylidene difluoride (PVDF) powder and inorganic matter micropowder with polyvinylidene difluoride (PVDF) powder/inorganic matter micropowder volume ratio, also has the additives polyethylene glycol powder, the molecular weight of described polyoxyethylene glycol powder is 600～20000, add-on is 0.5～1.5 times of polyvinylidene difluoride (PVDF) powder volume content, join in the solvent of 8～10 times of polyvinylidene difluoride (PVDF) powder volume, stir down fully at 78-82 ℃, dissolve fully to the polyvinylidene difluoride (PVDF) powder, obtain clarifying film-casting liquid; Described inorganic matter micropowder is a lime carbonate, and its particle diameter is 60～90nm or 0.8～1.6 μ m; Described solvent is a N,N-DIMETHYLACETAMIDE;
(2) standing and defoaming: with the film-casting liquid of (1) gained under 78～82 ℃, constant temperature standing and defoaming 2～3 hours;
(3) system film: the film-casting liquid that deaeration is finished is scraped on sheet glass and is made the flat sheet membrane that thickness is 100～150 μ m; Again the film of gained is immersed in steady temperature and is in 10～60 ℃ the ultrafiltration water precipitation bath, solidification forming, treat that film comes off from the sheet glass automatically after, can obtain described inorganic matter micropowder hybrid polyvinylidene fluoride.
2. the preparation method of inorganic matter micropowder hybrid polyvinylidene fluoride according to claim 1, the particle diameter that it is characterized in that described inorganic matter micropowder is 60～90nm.
3. the preparation method of inorganic matter micropowder hybrid polyvinylidene fluoride according to claim 1 and 2, the molecular weight that it is characterized in that described additives polyethylene glycol powder is 10000, add-on is 1.5 times of polyvinylidene difluoride (PVDF) powder volume content; The particle diameter of described inorganic matter micropowder is 60～90nm, and the volume ratio of itself and polyvinylidene difluoride (PVDF) powder is 1/1; Described coagulation bath temperature is 10 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100597811A CN100537644C (en) | 2007-09-26 | 2007-09-26 | Method for preparing inorganic matter micropowder hybrid polyvinylidene fluoride |
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| CN105289330B (en) * | 2015-12-01 | 2017-12-12 | 天津工业大学 | A kind of preparation method of cement hollow-fibre membrane as supporter |
| CN105771691A (en) * | 2016-05-10 | 2016-07-20 | 华中农业大学 | High-flux low-attenuation polyvinylidene fluoride separating membrane and preparation method |
| CN106731900A (en) * | 2017-01-12 | 2017-05-31 | 常州大学 | In-situ sol-gel high-strength polyvinylidene fluoride milipore filter and preparation method |
| CN113828166A (en) * | 2021-10-13 | 2021-12-24 | 无锡市道格环保科技有限公司 | Preparation method of organic separation membrane for extracting vegetable protein peptide |
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