CN102527249A - High-density polyethylene hollow fiber microporous membrane and preparation method thereof - Google Patents
High-density polyethylene hollow fiber microporous membrane and preparation method thereof Download PDFInfo
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- CN102527249A CN102527249A CN2011104274401A CN201110427440A CN102527249A CN 102527249 A CN102527249 A CN 102527249A CN 2011104274401 A CN2011104274401 A CN 2011104274401A CN 201110427440 A CN201110427440 A CN 201110427440A CN 102527249 A CN102527249 A CN 102527249A
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- hollow fiber
- microporous membrane
- density polyethylene
- fiber microporous
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Abstract
The invention discloses a high-density polyethylene hollow fiber microporous membrane and a preparation method thereof. The method is characterized by comprising the following process steps: melting spinning, cooling, winding, thermal treatment, cold stretching, thermal stretching, thermal sizing and testing. Polyethylene resin is performed with melting processing, and polyethylene melt flows out of a wire sprayer and is formed in stretching mode under effect of winding tension. The preparation method is low in device investment, small in energy consumption and free of environment pollution. Compared with other membrane materials, the prepared polyethylene hollow fiber microporous membrane is high in strength, resistant to serve conditions of acid, alkali and the like, resistant to corrosion of bacteria and the like, good in temperature resistance, in micropore state and in microcrack shape, causes no dissolve-out harmful substances in using process and can be stored in dry state.
Description
Technical field
The present invention relates to the film separation field, particularly relate to a kind of high density polyethylene (HDPE) hollow fiber microporous membrane and preparation method thereof.
Background technology
Film separates characteristics such as have the separative efficiency height, selectivity is good, energy consumption is low, non-secondary pollution, equipment investment are few, in industries such as chemical industry, oil, electronics, medical treatment, food, beverage, city tap-water engineering and environmental protection, is widely used.The mechanical strength of micropore polyolefin hollow-fibre membrane and chemical stability etc. are superior to cellulose acetate and derivatives membrane thereof, thereby purposes is very extensively like micro-filtration, ultrafiltration, film distillation, membrane extraction blood oxygen etc.Hollow-fibre membrane has many special excellent properties, more and more receives people's attention.
The characteristics of hollow fiber microporous membrane are to have very high loading density, and very big specific area can be provided, and this makes and under identical performance, compare with other forms of film that assembly volume is minimum.Membrane module is self supporting structure, need not to add in addition other supporter, can simplify the complexity of membrane module assembling greatly; Favorable reproducibility is amplified easily.Generally speaking, laboratory scale membrane module is compared with plant-scale membrane module, and liquid form wherein and separating effect difference are little; Flexibility: press and two kinds of filter types of external pressure in hollow-fibre membrane can according to circumstances be taked.Device miniaturization simplifies the structure.
Advantages such as the polyolefin hollow-fibre membrane has that micropore is even, separating property good, intensity is high, heatproof and corrosion resistance and good, wide application.
The polyethylene hollow fiber film is compared with polypropylene hollow fiber membrane, on performance, has more advantage, such as its porosity is high, gas permeation rate is big, corrosion-resistant and ageing-resistant performance is good, the life-span is longer etc.
And " solution wet spinning " that prior art for preparing polyolefin hollow-fibre membrane adopts; Use a large amount of solvents in the technological process, and the tunica fibrosa mechanical property that makes is relatively poor, in the post-processed to dicyandiamide solution reclaim, separation and recycle; Increase the equipment input, be prone to cause environmental pollution.
Summary of the invention
To the deficiency of prior art, the technical problem that quasi-solution of the present invention is determined provides a kind of high density polyethylene (HDPE) hollow fiber microporous membrane and preparation method thereof.
Technical scheme of the present invention is following:
The present invention is the preparation that stretching legal system film is applied to the high density polyethylene (HDPE) hollow fiber microporous membrane; Pulling method prepares hollow fiber microporous membrane; Be that utilization melt extrudes, the technology of hollow spinning moulding; Under the additive situation of (comprising solvent), make semi-crystalline polymer crystallization under stress field, form perpendicular to stress direction and the stratified pieces crystal structure that is arranged in parallel; After the heat treatment, it is stretched, produced the flaw shaped microcellular structure of mutual perforation; Carry out thermal finalization again and handle, can obtain the doughnut poromerics.
The melt spinning forming process has determined the microstructure of as-spun fibre, is the basis of stretching pore film forming.Adopt different spinning techniques, the microstructure of resulting as-spun fibre is different.The present invention adopts upward spinning technology, and upward spinning method and downward spinning are opposite, and upward spinning is that the melt thread is extruded from mould vertically upward, and under the winding tension effect, the cooling forming that is stretched finally obtains film forming and uses as-spun fibre.
The advantage of upward spinning technology is:
⑴ can spin the more resin of high molecular weight;
⑵ can spin the fiber of larger diameter;
⑶ can obtain physical dimension, porosity and molecularly oriented more uniformly;
⑷ can obtain higher permeation flux and mechanical strength.
A kind of method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane; Comprise following technological process: melt spinning, cooling, coiling, heat treatment, cold stretch, hot-stretch, heat setting; Polyethylene resin feedstock is after melt process; Polyethylene melt is extruded spinning nozzle by screw extruder, under the coiling tension, and drawing and forming.
The melt index of said polyvinyl resin is 0.3~5.5, is preferably 5.0~5.5.
The spinning temperature of said melt spinning is 170 ℃~220 ℃, is preferably 100 ℃~150 ℃, and spinning temperature is the temperature before melt flows out spinneret orifice, claims extrusion temperature again.
In the said cold wind technology, cooling air is preferably 280mm~330mm apart from spinning nozzle 150mm~350mm; Polyethylene melt leaves spinning head in the whole spinning process of reeling, and before the solidification point, is the transition stage of melt thread to the as-spun fibre conversion, also is fibroplastic most important phase, and this moment, the viscosity rising of melt was very fast, thereby cooling plays an important role.If cooling air is nearer from spinning nozzle; Then the melt thread is cooled after leaving spinneret immediately, and melt viscosity rises rapidly, and spinning head place tensile stress improves; The preorientation probability of spun filament fiber is bigger; Degree of crystallinity is higher, but this moment, formation was less perpendicular to the chain-folded lamellae of stress direction, thereby elastic recovery rate is lower; When cooling air when spinning nozzle is far away, polymer melt is extruded back viscosity and is risen slowlyer, thereby polymer molecular chain has certain relaxation time and is orientated its elastic recovery rate and birefringence rising; But the blowing position is too high, and the relaxation time of polymer molecular chain further prolongs, and the disorientation effect of macromolecular chain segment increases in the melt.
In the said cold wind technology, chilling temperature is 10 ℃~30 ℃.
The ratio range of convoluting speed and extrusion linear speed is 3000~4000 in the said technological process.The ratio of convoluting speed and extrusion linear speed is also claimed spinning/draw ratio.
The high density polyethylene (HDPE) hollow fiber microporous membrane that described preparation method makes, melt spinning adopts upward spinning technology, and polyethylene melt is extruded through spinning nozzle vertically upward.
The characterizing method of polyethylene hollow fiber microporous membrane material of the present invention and membrane structure, performance is following:
1, the degree of crystallinity of polyethylene (PE) fiber
With the melting enthalpy Δ H (J/g) of DSC6200 differential thermal analyzer (Seiko, Japan) mensuration PE, 10 ℃/min of the rate of heat addition,
50~250 ℃ of Range of measuring temp obtain the degree of crystallinity of doughnut through computes:
In the formula: Xc-degree of crystallinity; The melting enthalpy of Δ H-specimen; The melting enthalpy of Δ Hc-100% crystallization PE, 293.0 (J/g).
2, the elastic recovery rate of polyethylene (PE) fiber
With Gotech electronic universal tester (GT-T5-2000, Taiwan) the PE as-spun fibre of 20.0mm is stretched to 30.0 mm, rate of extension 10.0mm/min, stretch stop after, take off sample, test its resilience length, by the elastic recovery rate of computes sample:
3, the mensuration of birefringence
Adopt the number of interference fringes and the offset angle of XPL-1 petrographic microscope (optical instrument factory, the south of the River, Nanjing of China) test PE doughnut spun filament, then according to its birefringence of computes:
In the formula: n is a number of interference fringes, and θ is an offset angle, and λ is a lambda1-wavelength.
4, mechanical property
The stress-strain behavior of PE hollow fiber microporous membrane during with Gotech electronic universal tester (GT-T5-2000, Taiwan) test room temperature, rate of extension 50mm/min.
5, porosity and pore-size distribution
Adopt Autopore IV 9510 full-automatic mercury injection apparatus (Micromerica Instrument Corp.; USA) measuring the maximum of PE hollow fiber microporous membrane can several aperture, porosity and pore-size distribution; Pressure limit 0.5Psia-6000Psia, the image data of boosting step by step.
In addition; The porosity of PE hollow-fibre membrane that also adopted dried wet film gravimetric detemination; Being about to the PE hollow-fibre membrane that weight is
immerses in the reagent
of ability wetting film material; Film is fully soaked into; Sonicated; With air emptying in the film; Make reagent be full of fenestra fully; Dry outer wall after the taking-up, rapidly wet film is weighed
, with the porosity of computes institute micrometer pore membrane:
-open-cell porosity %;
-dry film is heavy;
-wet film is heavy; The density of
-film,
-reagent density.
6, Morphological analysis of structure
Employing Dimension3100 type scanning probe microscopy (di Digital Instruments, USA), the inside and outside wall construction of Nanoscope III a controller test PE doughnut spun filament.
7, N2 flux
140 PE doughnuts are made U-shaped, and openend is fixed with epoxy resin, and the length that fiber is enclosed resin is about 2.5 centimetres, and the effective length of doughnut is 5~9 centimetres, makes sample.Use homemade N2 measurement mechanism then, the N2 throughput of passing through under the different pressures when measuring room temperature calculates the N2 flux of PE hollow fiber microporous membrane through the film internal surface area, representes the L/ of unit (m2 h 0.1MPa) with FN.
8, water flux
Method with measuring the N2 flux is similar, and 100 PE hollow fiber microporous membranes are made sample, and its effective length is 9 centimetres.Mixed solution (volume ratio 75/25) sonicated of immersion second alcohol and water 30 minutes makes its hydrophiling, fully washs with deionized water then; Keep at the hydraulic pressure of 0.1MPa, measuring the flow that water passes through from outer wall under the moistening situation of fiber; Internal surface area with film is calculated water flux; Be ultrafiltration rate, represent, the l/ of unit (m2 h0.1MPa) with UFR.
Adopt " melt spinning pulling method " preparation polyethylene hollow fiber microporous barrier, compare with " solution wet spinning ", equipment investment is little, and energy consumption is little, non-environmental-pollution.The polyethylene hollow fiber microporous barrier that makes is compared with other membrane materials, on performance, has following advantage:
1. intensity is high.Fracture strength>10.0 MPa, because compressive resistance is high, so the long service life of film;
Corrosion such as 2. harsh conditions such as acid and alkali resistance, and anti-bacterium;
3. heat resistance is good.Under the fixing situation in two ends, can in-l0 ℃~100 ℃ of scopes, normally use.And < 45 ℃ of the serviceability temperatures of the plain film of polysulfone fibre;
4. the micropore form is the micro-crack type, and flux ratio garden pass film is big when identical rejection, and during identical flux, its rejection is then high than garden pass;
5. can prepare hydrophobic, hydrophilic and compound various series membranes parting material, wide application.The cellulose family film is a kind of hydrophilic film;
6. the microporous barrier that is obtained by melt spinning-pull stretching does not contain any additives, does not in use have harmful material stripping;
7. but dry state is preserved.
Description of drawings
Fig. 1 is the technological process of preparation polyethylene hollow fiber film;
Fig. 2 is that embodiment 1 gained polyethylene hollow fiber microporous barrier inwall amplifies 6000 times of electron-microscope scanning figure;
Fig. 3 is that embodiment 1 gained polyethylene hollow fiber microporous barrier outer wall amplifies 6000 times of electron-microscope scanning figure;
Fig. 4 is that embodiment 2 gained polyethylene hollow fiber microporous barrier inwalls amplify 6000 times of electron-microscope scanning figure;
Fig. 5 is that embodiment 2 gained polyethylene hollow fiber microporous barrier outer walls amplify 6000 times of electron-microscope scanning figure.
The specific embodiment
Embodiment 1:
Choosing molecular weight is 1.0 (Mn) * 10
-5Polyvinyl resin, density is 0.995kg/m
3, melt index 1.1; Technological process is: melt spinning, cooling, coiling, heat treatment, cold stretch, hot-stretch, heat setting, test.Polyvinyl resin is after melt process, and polyethylene melt is extruded spinning nozzle by screw extruder, under the coiling tension, and drawing and forming.Spinning temperature adopts 180 ℃ in 1 district, 200 ℃ in 2 districts, 220 ℃ in 3 districts; Spinning/traction speed ratio is 3000; The high 330mm of cooling air, 10 ± 5 ℃ of cooling wind-warm syndrome; The polyethylene hollow fiber microporous barrier performance that obtains is following: porosity 79.53%, aperture 40.6nm, specific area 451.39m
2/ g, apparent density 0.681g/cm
3, fracture strength 58.6MPa, N
2Flux 49 * 103L/m
2H0.1MPa, water flux are 227L/ m
2H0.1MPa.
Embodiment 2
Choosing molecular weight is 5.0 (Mn) * 10
-5Polyvinyl resin, density is 0.966kg/m3, melt index 1.08; Technological process is: melt spinning, cooling, coiling, heat treatment, cold stretch, hot-stretch, heat setting, test.Polyvinyl resin is after melt process, and polyethylene melt is extruded spinning nozzle by screw extruder, under the coiling tension, and drawing and forming.Spinning temperature adopts 190 ℃ in 1 district, 210 ℃ in 2 districts, 225 ℃ in 3 districts; Spinning/traction speed ratio is 4000; The high 300mm of cooling air, 10 ± 5 ℃ of cooling wind-warm syndrome; The polyethylene hollow fiber microporous barrier performance that obtains is following: porosity 75.1%, aperture 33.2nm, specific area 288.94m
2/ g, apparent density 0.699g/cm
3, fracture strength 60.3MPa, N
2Flux 47 * 103L/m
2H0.1MPa, water flux are 220L/ m
2H0.1MPa.
The above; Be merely the preferable specific embodiment of the present invention; But protection scope of the present invention is not limited thereto; Any technical staff who is familiar with the present technique field is equal to replacement or change according to technical scheme of the present invention and inventive concept thereof in the technical scope that the present invention discloses, all should be encompassed within protection scope of the present invention.
Claims (10)
1. method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane; It is characterized in that comprising following technological process: melt spinning, cooling, coiling, heat treatment, cold stretch, hot-stretch, heat setting, test; Polyvinyl resin is after melt process; Polyethylene melt is extruded spinning nozzle by screw extruder, under the coiling tension, and drawing and forming.
2. the method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane as claimed in claim 1 is characterized in that, the melt index of said polyvinyl resin is 0.3~5.5.
3. the method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane as claimed in claim 2 is characterized in that, the melt index of said polyvinyl resin is 5.0~5.5.
4. like any described method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane of claim 1-3, it is characterized in that the spinning temperature of said melt spinning is 170 ℃~220 ℃.
5. the method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane as claimed in claim 4 is characterized in that, said heat treated treatment temperature is 100 ℃~150 ℃.
6. the method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane as claimed in claim 5 is characterized in that, in the said cold wind technology, cooling air is apart from spinning nozzle 150mm~350mm.
7. like claim 5 or the 6 described methods that prepare the high density polyethylene (HDPE) hollow fiber microporous membrane, it is characterized in that in the said cold wind technology, the cooling air air supply position is apart from spinning nozzle 280mm~330mm.
8. the method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane as claimed in claim 7 is characterized in that, in the said cold wind technology, chilling temperature is 10 ℃~30 ℃.
9. the method for preparing the high density polyethylene (HDPE) hollow fiber microporous membrane as claimed in claim 8 is characterized in that, the ratio range of convoluting speed and extrusion linear speed is 3000~4000 in the said technological process.
10. the high density polyethylene (HDPE) hollow fiber microporous membrane that makes like the described preparation method of claim 1-9 is characterized in that, said melt spinning adopts upward spinning technology, and said polyethylene melt is extruded through spinning nozzle vertically upward.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103057111A (en) * | 2012-12-20 | 2013-04-24 | 天邦膜技术国家工程研究中心有限责任公司 | Polyethylene hollow fiber microporous film cold and hot stretching device and stretching technology thereof |
CN103551046A (en) * | 2013-11-11 | 2014-02-05 | 天津风云水资源科技有限公司 | Preparation method for hydrophobic ammonia nitrogen removal film |
CN104821416A (en) * | 2015-04-21 | 2015-08-05 | 长兴铁鹰电气有限公司 | Lead-acid storage battery electrolyte preparation device |
CN105498555A (en) * | 2014-09-24 | 2016-04-20 | 中国石油化工股份有限公司 | Production method of thermoplastic high-molecular material hollow fiber micro-pore membrane |
CN110681269A (en) * | 2019-11-20 | 2020-01-14 | 宁波建嵘科技有限公司 | Two-stage coating heterogeneous synchronous composite membrane preparation technology and device |
CN110917908A (en) * | 2019-10-11 | 2020-03-27 | 贵州理工学院 | Hydrophilic polymer composite hollow fiber membrane with double microporous structures and preparation method thereof |
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CN1654113A (en) * | 2005-01-27 | 2005-08-17 | 浙江大学 | Hydrophilic modified preparation method for polyethylene hollow fiber microporous membrane |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103057111A (en) * | 2012-12-20 | 2013-04-24 | 天邦膜技术国家工程研究中心有限责任公司 | Polyethylene hollow fiber microporous film cold and hot stretching device and stretching technology thereof |
CN103551046A (en) * | 2013-11-11 | 2014-02-05 | 天津风云水资源科技有限公司 | Preparation method for hydrophobic ammonia nitrogen removal film |
CN103551046B (en) * | 2013-11-11 | 2016-03-23 | 天津风云水资源科技有限公司 | A kind of preparation method of hydrophobic ammonia nitrogen removal film |
CN105498555A (en) * | 2014-09-24 | 2016-04-20 | 中国石油化工股份有限公司 | Production method of thermoplastic high-molecular material hollow fiber micro-pore membrane |
CN104821416A (en) * | 2015-04-21 | 2015-08-05 | 长兴铁鹰电气有限公司 | Lead-acid storage battery electrolyte preparation device |
CN110917908A (en) * | 2019-10-11 | 2020-03-27 | 贵州理工学院 | Hydrophilic polymer composite hollow fiber membrane with double microporous structures and preparation method thereof |
CN110681269A (en) * | 2019-11-20 | 2020-01-14 | 宁波建嵘科技有限公司 | Two-stage coating heterogeneous synchronous composite membrane preparation technology and device |
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Application publication date: 20120704 |