CN102580571A - Method for preparing ultra high molecular weight polyethylene micro-filtration membrane - Google Patents
Method for preparing ultra high molecular weight polyethylene micro-filtration membrane Download PDFInfo
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Abstract
The invention relates to a method for preparing an ultra high molecular weight polyethylene micro-filtration membrane. The method comprises the following steps of: (1) weighing and mixing 10 to 30 weight parts of ultra high molecular weight polyethylene, 67 to 89.4 weight parts of thinning agent, 0.1 to 2 weight parts of nucleating agent and 0.5 to 1 part of antioxidant, and treating the obtained mixture to obtain a flat membrane by a die pressing process or an extrusion process; (2) orienting the nucleating agent by adopting a shearing process or a stretching process to obtain an oriented flat membrane; (3) removing the thinning agent by using an extracting agent, washing, drying, and thus obtaining a micropore membrane; and (4) drying, annualizing and sizing the micropore membrane, and thus obtaining the ultra high molecular weight polyethylene micro-filtration membrane. Compared with the prior art, the method has the advantages that: the prepared ultra high molecular weight polyethylene micropore membrane has regular form, uniform aperture distribution and high water flux, has predominant mechanical properties, and particularly has high elongation at break in the orientation direction.
Description
Technical field
The invention belongs to the membrane separation technique field, relate in particular to a kind of preparation of ultra-high molecular mass polyethylene micropore film, the ultra-high molecular mass polyethylene micropore film that makes is satisfied with the requirement of the micro-filtration membrane material in the water treatment procedure.
Background technology
Micro-filtration is a kind of important film separation process, is widely used in industries such as trade effluent processing, drinking water preparation, food industry, health care, military project.The basic important document of film separation process is a filter assemblies, and core is the filter membrane in the assembly, and is main with micropore filtering film and the assembly that high-molecular organic material is processed.According to the mean size or the trapped particles size of fenestra, film separates can be divided into various procedures, and wherein the definition pore size of micro-filtration is about 0.1-100um, particulate, protein and bacterium etc. in the main trap water.Common diffusion barrier has three kinds of flat sheet membrane, tubular membrane, hollow-fibre membrane.
The method for preparing polymer microporous film is a lot, for example immersion precipitation, phase separation method, pulling method etc.Wherein thermally induced phase separation (TIPS) is important and the method for extensive use, and it is applicable to that preparation can not find the polymer of good solvent at normal temperatures, and especially many crystallizations perhaps have the polymer of hydrogen bond; The TIPS method is come the phase-splitting of induced polymer solution through heat exchange fast simultaneously, and the control process conditions can obtain various pore structure.The summary of TIPS process is: some thermoplasticity, crystalline high polymer and some high boiling diluent are at high temperature formed homogeneous phase solution earlier, reduce system temperature then, induce system generation solid-liquid (S-L) or liquid-liquid (L-L) to be separated; Can prepare polymer porous film after extraction removes diluent behind the system cooling curing.Described diluent is meant for polymeric material it is a kind potential solvent, is solvent when being non-solvent but high temperature at normal temperatures, i.e. " high temperature is compatible, the low temperature phase-splitting ".Diluent kind and content are most important factors in the TIPS film-forming process, and final membrane structure and film properties are had significant effects.Often pass through the drafting of the phasor of polymer-diluent, come at large to study the pore-forming dynamic process of various polymerization thing-diluent system.
At present, adopt the TIPS legal system to be equipped with polymeric film material and mainly concentrate on high density polyethylene (HDPE) (HDPE), polypropylene (PP), Kynoar (PVDF) etc.Ultra-high molecular weight polyethylene is because its excellent mechanical property, biocompatibility and chemical stability; Fabulous rub resistance and shock resistance; Make the ultra-high molecular mass polyethylene micropore film mechanical strength for preparing big; Stable in the medium-term and long-term serviceability of sewage disposal, be difficult for overall characteristics such as degraded.Because ultra-high molecular weight polyethylene is elastomeric state when fusion, almost do not have mobile.The TIPS method is that the preparation of ultra-high molecular mass polyethylene micropore film provides possibility.But the TIPS method is come the phase-splitting of induced polymer solution through heat exchange fast, makes the microporous barrier pore-size distribution for preparing inhomogeneous.
Summary of the invention
The object of the invention is exactly the preparation method that a kind of even aperture distribution, water flux is high, mechanical property is excellent ultra-high molecular weight polyethylene micro-filtration membrane are provided in order to overcome the defective that above-mentioned prior art exists.
The object of the invention can be realized through following technical scheme: a kind of preparation method of ultra-high molecular weight polyethylene micro-filtration membrane is characterized in that this method may further comprise the steps:
(1) content takes by weighing ultra-high molecular weight polyethylene 10-30 weight portion, diluent 67-89.4 weight portion, nucleator 0.1-2 weight portion and the mixing of antioxidant 0.5-1 weight portion by weight, and the gained mixture obtains flat sheet membranes through mould pressing process or expressing technique;
(2) adopt shearing technology or drawing process, nucleator is orientated, obtain being orientated flat sheet membranes;
(3) use extractant to remove diluent, after washing, drying, promptly form microporous barrier;
(4) microporous barrier is carried out drying and annealing typing, promptly prepare the ultra-high molecular weight polyethylene micro-filtration membrane.
The molecular weight of described ultra-high molecular weight polyethylene is 150～5,000,000.
Described nucleator is silica (SiO
2), titanium dioxide (TiO
2), CNT (CNT), Graphene, 2,4, a kind of in 6-Triaminopyrimidine (TP), malonyl urea (BA) or the glucitols nucleator;
Described diluent is selected from one or more in short chain alkanes kind solvent or the phthalate solvent;
Described antioxidant is selected from the combination of any or several kinds in organic tin antioxidant and/or the metallic soap kind antioxidant.
Described glucitols nucleator comprises 1,3:2,4-dibenzal sorbitol (DBS), 1,3:2, two pairs of methyl benzals of 4-sorbierite (MDBS) or 1,3:2,4-two (3, the 4-dimethyl) benzal sorbierite (DMDBS);
Described short chain alkanes kind solvent comprises octane, decane, paraffin oil, solid paraffin or atoleine; Described phthalate solvent comprises phthalic acid ester dimethyl ester, phthalic acid ester diethylester, phthalic acid ester dibutyl ester, phthalic acid ester dihexyl, phthalic acid ester dioctyl ester, phthalic acid ester di-isooctyl, phthalic acid ester two isodecyl esters, phthalic acid ester two (the own ester of 2-methyl) or dicyclohexyl phthalate;
Described organic tin antioxidant comprises dibutyl tin laurate, maleic acid dioctyltin, two (butyl maleate) two fourth tin, two (lauryl mercaptan) dibutyl tin, S, S '-two (the different hot tin of sulfo-Glycolic acid) dibutyl tin or Bis(lauroyloxy)dioctyltin; Described metallic soap kind antioxidant comprises calcium stearate, dolomol, lithium stearate, zinc stearate, aluminum stearate, double stearic acid aluminium, calcium laurate, zinc laurate, ricinoleic acid calcium or 2 ethyl hexanoic acid zinc.
The described mould pressing process of step (1) adopts following steps: adopt the direct molten mixture of Haake torque rheometer; Again through press mold machine compression molding flat sheet membranes; Haake torque rheometer melt mix temperature is 160～180 ℃, and molding temperature is 160～170 ℃.
The described expressing technique of step (1) adopts following steps: with mixture fusion in double screw extruder, mix and extrude; Obtain annotating film liquid; To annotate film liquid then through T type membrana oralis; Curtain coating is the molding plate film on the metal roller, and the processing temperature that twin-screw squeezes machine is 170～200 ℃, and screw speed is 200～400rpm.
The described shearing process using of step (2) following steps: through torque rheometer flat sheet membranes is heated to 125～145 ℃ of shear temperature, the control shear rate is 10～50s
-1, strain amplitude is 20～100%, obtains being orientated flat sheet membranes.
The described drawing process of step (2) adopts following steps: with the flat sheet membranes stretch orientation, draft temperature is 40～100 ℃ through the controlled universal electrical puller system of draft temperature, and rate of extension is 50～100mm/min, and elongation strain is 100～300%.
The described extractant of step (3) is selected from the one or more combination in absolute ethyl alcohol, glycerine, n-butanol or the chloroform.
The described drying of step (4) is 80 ℃ with the baking temperature of annealing typing, and be 3h drying time, and annealing temperature is 110 ℃, and annealing time is 10h.
In the TIPS method, add nucleator for crystalline polymer, its effect has three: one, accelerates the crystalline rate of polymer, thus control is separated, and then influence the dynamic process of film forming; The 2nd, improve crystallinity of polymer, help to improve mechanical strength and the hear resistance of material etc.; The 3rd, improve grain density, thus the aperture that reduces last microporous barrier.As everyone knows, the microporous barrier aperture reduces, and must be accompanied by the increase of water circulation path in film, and water flux reduces.Moreover the nano inorganic nucleator is very easily reunited, and other disperses to be difficult to realize the primary particle level generally speaking, thereby is difficult to embody the property of nano particle.Therefore, mixed polymer/diluent/nucleator not only can't improve water flux simply, and more is difficult to realize the nucleator fine dispersion.Simultaneously, the incompatible boundary of existence also can cause the deterioration of film article mechanical property.Therefore the dispersion that improves nucleator, the short polymer microporous film of preparation water stream channel is that the TIPS legal system is equipped with one of key technology of microporous barrier.
The present invention is employed in organic micromolecule compound, CNT and the SiO that is self-assembled into nanofiber in diluent and the ultra-high molecular weight polyethylene melt
2As nucleator, at a certain temperature, shearing that applies or stretching flow field are orientated nucleator, induce the UHMWPE crystallization, and utilize the TIPS legal system to be equipped with the ultra-high molecular mass polyethylene micropore film.Nucleator can generate homogeneous phase solution in most of diluents and polymer melt under hot conditions.After applying shearing or stretching flow field, not only improved the dispersion of nucleator, and made nucleator form orientation texture.The nucleator of orientation not only plays the effect of induced crystallization, and makes the vertical nucleator differently-oriented directivity growth of polymer platelet, the polymer microporous film that obtains being orientated.Therefore, to the TIPS technology of orientation ultra-high molecular mass polyethylene micropore film, nucleator and processing technology that the present invention selects have following characteristic: three kinds of difform nucleators (spherical, bar-shaped and fibrous) are selected in (1); (2) for ultra-high molecular weight polyethylene, diluent, nucleator and antioxidant homogeneous phase solution, before polymer crystallization, the flow field that applies is orientated nucleator; (3) under the prerequisite of effectively control orientation ultra-high molecular mass polyethylene micropore membrane pore structure and film properties, use a spot of nucleator as far as possible.
Compared with prior art; The present invention adds nucleator in polymer and diluent; High temperature applies and shears or the stretching flow field makes the nucleator orientation then; Not only improved nucleator and in polymer/diluent, disperseed, and the nucleator of orientation induces the UHMWPE crystallization of growing nonparasitically upon another plant, obtain the UHMWPE microporous barrier of apparent height orientation.Compare with the UHMWPE microporous barrier that does not have orientation, the UHMWPE microporous barrier pore-size distribution after the orientation is littler, water flux is high, mechanical property is excellent more.Therefore, the microporous barrier of the present invention's preparation can be used for food, medicine, PREPARATION OF ULTRA-PURE WATER, satisfies the requirement that separates, purifies, concentrates and purify.
Description of drawings
The not orientation UHMWPE microporous barrier surface SEM aspect graph that Fig. 1 obtains for Comparative Examples 1;
The orientation UHMWPE microporous barrier surface SEM aspect graph that Fig. 2 obtains for embodiment 1;
Fig. 3 is the influences of the different nucleators that obtain of Comparative Examples 1, embodiment 1 and Comparative Examples to UHMWPE microporous barrier water flux;
Fig. 4 is the influences of the different nucleators that obtain of Comparative Examples 3, embodiment 2, embodiment 4, embodiment 6 to UHMWPE microporous barrier mechanical property.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Comparative Examples 1
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 10% weight fraction, the DBS of 0.1% weight fraction, the atoleine of 89.4% weight fraction, the antioxidant maleic acid dibutyl tin melting mixing of 0.5% weight fraction, obtain the ultra-high molecular weight polyethylene mixture.The melt mix temperature of Haake torque rheometer is 160 ℃, and the melting mixing time is 12min, and rotor speed is 80rpm.
(2) then with ultra-high molecular weight polyethylene mixture molding plate film on the press mold machine.Film thickness is controlled at 200um, and molding temperature is 160 ℃, and clamp time is 5min.
(3) then use absolute ethyl alcohol extraction liquids paraffin, use the deionized water cyclic washing, promptly form microporous barrier after the drying.
(4) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
Comparative Examples 2
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 20% weight fraction, the CNT of 1% weight fraction, the atoleine of 78% weight fraction, the antioxidant maleic acid dibutyl tin melting mixing of 1% weight fraction, obtain the ultra-high molecular weight polyethylene mixture.Melt mix temperature is 170 ℃, and the melting mixing time is 12min, and rotor speed is 80rpm.
(2) with ultra-high molecular weight polyethylene mixture compression molding flat sheet membranes.Film thickness is controlled at 200um, and molding temperature is 170 ℃, and clamp time is 5min, and pressure is 5MPa.
(3) then use absolute ethyl alcohol extraction liquids paraffin, suitably wash, promptly form microporous barrier after the drying through deionized water.
(4) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
Comparative Examples 3
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 30% weight fraction, the SiO of 2% weight fraction
2, the atoleine of 67% weight fraction, the antioxidant maleic acid dibutyl tin melting mixing of 1% weight fraction, obtain the ultra-high molecular weight polyethylene mixture.Melt mix temperature is 170 ℃, and the melting mixing time is 12min, and rotor speed is 80rpm.
(2) with ultra-high molecular weight polyethylene mixture compression molding flat sheet membranes.Film thickness is controlled at 200um, and molding temperature is 170 ℃, and clamp time is 5min, and pressure is 5MPa.
(3) then use absolute ethyl alcohol extraction liquids paraffin, suitably wash, promptly form microporous barrier after the drying through deionized water.
(4) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 10% weight fraction, the DBS of 0.1% weight fraction; The antioxidant maleic acid dibutyl tin melting mixing of the atoleine of 89.4% weight fraction, 0.5% weight fraction obtains the ultra-high molecular weight polyethylene mixture.Melt mix temperature is 170 ℃, and the melting mixing time is 16min, and rotor speed is 80rpm.
(2) with ultra-high molecular weight polyethylene mixture compression molding flat sheet membranes.Film thickness is controlled at 200um, and pressure is 5MPa, and molding temperature is 170 ℃, and clamp time is 6min.
(3) use torque rheometer that the molding plate film is applied and shear the flow field.Shear temperature is 125 ℃, and shear rate is 50s
-1, strain amplitude is 100%.
(4) then use absolute ethyl alcohol extraction liquids paraffin, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 30% weight fraction, the DMDBS of 1% weight fraction, the atoleine of 68% weight fraction, the antioxidant maleic acid dibutyl tin melting mixing of 1% weight fraction, obtain the ultra-high molecular weight polyethylene mixture.Melt mix temperature is 170 ℃, and the melting mixing time is 16min,, rotor speed is 80rpm.
(2) with ultra-high molecular weight polyethylene mixture compression molding flat sheet membranes.Film thickness is controlled at 200um, and pressure is 5MPa, and molding temperature is 170 ℃, and clamp time is 6min.
(3) use the electronic universal cupping machine that the molding plate film is applied the stretching flow field.Draft temperature is 40 ℃, and rate of extension is 100mm/min, and elongation strain is 300%.
(4) then use absolute ethyl alcohol extraction liquids paraffin, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 10% weight fraction, the CNT of 0.5% weight fraction; The antioxidant maleic acid dibutyl tin melting mixing of the atoleine of 89% weight fraction, 0.5% weight fraction obtains the ultra-high molecular weight polyethylene mixture.Melt mix temperature is 170 ℃, and the melting mixing time is 16min, and rotor speed is 80rpm.
(2) with ultra-high molecular weight polyethylene mixture compression molding flat sheet membranes.Film thickness is controlled at 200um, and pressure is 5MPa, and molding temperature is 170 ℃, and clamp time is 6min.
(3) use torque rheometer that the molding plate film is applied and shear the flow field.Shear temperature is 130 ℃, and shear rate is 50s
-1, strain amplitude is 100%.
(4) then use absolute ethyl alcohol extraction liquids paraffin, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 30% weight fraction, the CNT of 2% weight fraction, the atoleine of 67% weight fraction, the antioxidant maleic acid dibutyl tin melting mixing of 1% weight fraction, obtain the ultra-high molecular weight polyethylene mixture.Melt mix temperature is 170 ℃, and the melting mixing time is 16min, and rotor speed is 80rpm.
(2) with ultra-high molecular weight polyethylene mixture compression molding flat sheet membranes.Film thickness is controlled at 200um, and pressure is 5MPa, and molding temperature is 170 ℃, and clamp time is 6min.
(3) use the electronic universal cupping machine that the molding plate film is applied the stretching flow field.Draft temperature is 40 ℃, and rate of extension is 100mm/min, and elongation strain is 300%.
(4) then use absolute ethyl alcohol extraction liquids paraffin, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 10% weight fraction, the SiO of 0.5% weight fraction
2, the antioxidant maleic acid dibutyl tin melting mixing of the atoleine of 89% weight fraction, 0.5% weight fraction obtains the ultra-high molecular weight polyethylene mixture.Melt mix temperature is 170 ℃, and the melting mixing time is 16min, and rotor speed is 80rpm.
(2) with ultra-high molecular weight polyethylene mixture compression molding flat sheet membranes.Film thickness is controlled at 200um, and pressure is 5MPa, and molding temperature is 170 ℃, and clamp time is 6min.
(3) use torque rheometer that the molding plate film is applied and shear the flow field.Shear temperature is 130 ℃, and shear rate is 50s
-1, strain amplitude is 100%.
(4) then use absolute ethyl alcohol extraction liquids paraffin, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
(1) passes through the Haake torque rheometer with the ultra-high molecular weight polyethylene of 30% weight fraction, the SiO of 2% weight fraction
2, the atoleine of 67% weight fraction, the antioxidant maleic acid dibutyl tin melting mixing of 1% weight fraction, obtain the ultra-high molecular weight polyethylene mixture.Melt mix temperature is 170 ℃, and the melting mixing time is 16min, and rotor speed is 80rpm.
(2) with ultra-high molecular weight polyethylene mixture compression molding flat sheet membranes.Film thickness is controlled at 200um, and pressure is 5MPa, and molding temperature is 170 ℃, and clamp time is 6min.
(3) use the electronic universal cupping machine that the molding plate film is applied the stretching flow field.Draft temperature is 40 ℃, and rate of extension is 100mm/min, and elongation strain is 300%.
(4) then use absolute ethyl alcohol extraction liquids paraffin, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
Embodiment 7
(1) at first utilizes the ultra-high molecular weight polyethylene of double screw extruder expressing technique melting mixing 15% weight fraction, the MDBS of 0.5% weight fraction, the phthalic acid ester dioctyl ester of 84% weight fraction, the antioxidant maleic acid dibutyl tin of 0.5% weight fraction, obtain annotating film liquid.The screw rod extrusion temperature is 170～190 ℃, screw speed 350rpm.
(2) make notes film liquid under pressure through a T-type membrana oralis, curtain coating is the molding plate film on the metal roller.Die temperature is 130～140 ℃, and the metal roller temperature is 25～35 ℃.
(3) use torque rheometer that the molding plate film is applied and shear the flow field.Shear temperature is 130 ℃, and shear rate is 50s
-1, strain amplitude is 100%.
(4) then use absolute ethyl alcohol extraction phthalic acid ester dioctyl ester, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
Embodiment 8
(1) at first utilizes the ultra-high molecular weight polyethylene of double screw extruder expressing technique melting mixing 20% weight fraction, the CNT of 1% weight fraction, the phthalic acid ester dioctyl ester of 78% weight fraction, the antioxidant maleic acid dibutyl tin of 1% weight fraction, obtain annotating film liquid.The screw rod extrusion temperature is 170～190 ℃, screw speed 350rpm.
(2) make notes film liquid under pressure through a T-type membrana oralis, curtain coating is the molding plate film on the metal roller.Die temperature is 130～140 ℃, and the metal roller temperature is 25～35 ℃.
(3) use the electronic universal cupping machine that the molding plate film is applied the stretching flow field.Draft temperature is 40 ℃, and rate of extension is 100mm/min, and elongation strain is 300%.
(4) then use absolute ethyl alcohol extraction phthalic acid ester dioctyl ester, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
Embodiment 9
(1) at first utilizes the ultra-high molecular weight polyethylene of double screw extruder expressing technique melting mixing 20% weight fraction, the SiO of 1% weight fraction
2, the phthalic acid ester dioctyl ester of 78% weight fraction, the antioxidant maleic acid dibutyl tin of 1% weight fraction, obtain annotating film liquid.The screw rod extrusion temperature is 170～190 ℃, screw speed 350rpm.
(2) make notes film liquid under pressure through a T-type membrana oralis, curtain coating is the molding plate film on the metal roller.Die temperature is 130～140 ℃, and the metal roller temperature is 25～35 ℃.
(3) use the electronic universal cupping machine that the molding plate film is applied the stretching flow field.Draft temperature is 40 ℃, and rate of extension is 100mm/min, and elongation strain is 300%.
(4) then use absolute ethyl alcohol extraction phthalic acid ester dioctyl ester, suitably wash, promptly form microporous barrier after the drying through deionized water.
(5) use baking oven that microporous barrier is carried out drying and annealing typing at last, can obtain the ultra-high molecular weight polyethylene micro-filtration membrane.Baking temperature is 80 ℃, and be 3 hours drying time, 110 ℃ of annealing temperatures, and annealing time is 10 hours.
Ultra-high molecular weight polyethylene micro-filtration membrane of the present invention also can prepare under following condition: adopt the step the same with embodiment 1～9, difference is different shearings or stretching condition, and specifically process is seen and shown 1-2:
Table 1
Table 2
Fig. 1 and 2 is respectively the 10%UHMWPE microporous barrier surface SEM photo that Comparative Examples 1 and embodiment 1 obtain.From photo, can find out, because the orientation of DBS fiber is induced the UHMWPE crystallization of growing nonparasitically upon another plant, obtain pore-size distribution anisotropy UHMWPE microporous barrier more uniformly among the embodiment 1.
Fig. 3 is to 10%UHMWPE, does not have the influence to UHMWPE microporous barrier water flux of orientation and orientation.Can find out obviously that by figure the alignment films water flux has improved 3～4 times.
Fig. 4 is to 30%UHMWPE, does not have the influence to UHMWPE microporous barrier differently-oriented directivity mechanical property of orientation and orientation.For alignment films, along differently-oriented directivity, stress and strain all is improved to some extent.
Claims (10)
1. the preparation method of a ultra-high molecular weight polyethylene micro-filtration membrane is characterized in that, this method may further comprise the steps:
(1) content takes by weighing ultra-high molecular weight polyethylene 10-30 weight portion, diluent 67-89.4 weight portion, nucleator 0.1-2 weight portion and the mixing of antioxidant 0.5-1 weight portion by weight, and the gained mixture obtains flat sheet membranes through mould pressing process or expressing technique;
(2) adopt shearing technology or drawing process, nucleator is orientated, obtain being orientated flat sheet membranes;
(3) use extractant to remove diluent, after washing, drying, promptly form microporous barrier;
(4) microporous barrier is carried out drying and annealing typing, promptly prepare the ultra-high molecular weight polyethylene micro-filtration membrane.
2. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 1 is characterized in that, the molecular weight of described ultra-high molecular weight polyethylene is 150～5,000,000.
3. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 1 is characterized in that, described nucleator is a silica; Titanium dioxide, CNT, Graphene; 2,4, a kind of in 6-Triaminopyrimidine, malonyl urea or the glucitols nucleator;
Described diluent is selected from one or more in short chain alkanes kind solvent or the phthalate solvent;
Described antioxidant is selected from the combination of any or several kinds in organic tin antioxidant and/or the metallic soap kind antioxidant.
4. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 3 is characterized in that, described glucitols nucleator comprises 1; 3:2,4-dibenzal sorbitol, 1,3:2; 4-two pairs of methyl benzals sorbierite or 1; 3:2,4-two (3, the 4-dimethyl) benzal sorbierite;
Described short chain alkanes kind solvent comprises octane, decane, paraffin oil, solid paraffin or atoleine; Described phthalate solvent comprises phthalic acid ester dimethyl ester, phthalic acid ester diethylester, phthalic acid ester dibutyl ester, phthalic acid ester dihexyl, phthalic acid ester dioctyl ester, phthalic acid ester di-isooctyl, phthalic acid ester two isodecyl esters, phthalic acid ester two (the own ester of 2-methyl) or dicyclohexyl phthalate;
Described organic tin antioxidant comprises dibutyl tin laurate, maleic acid dioctyltin, two (butyl maleate) two fourth tin, two (lauryl mercaptan) dibutyl tin, S, S '-two (the different hot tin of sulfo-Glycolic acid) dibutyl tin or Bis(lauroyloxy)dioctyltin; Described metallic soap kind antioxidant comprises calcium stearate, dolomol, lithium stearate, zinc stearate, aluminum stearate, double stearic acid aluminium, calcium laurate, zinc laurate, ricinoleic acid calcium or 2 ethyl hexanoic acid zinc.
5. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 1; It is characterized in that; The described mould pressing process of step (1) adopts following steps: adopt the direct molten mixture of Haake torque rheometer; Through press mold machine compression molding flat sheet membranes, Haake torque rheometer melt mix temperature is 160～180 ℃ again, and molding temperature is 160～170 ℃.
6. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 1; It is characterized in that the described expressing technique of step (1) adopts following steps: with mixture fusion in double screw extruder, mix and extrude, obtain annotating film liquid; To annotate film liquid then through T type membrana oralis; Curtain coating is the molding plate film on the metal roller, and the processing temperature that twin-screw squeezes machine is 170～200 ℃, and screw speed is 200～400rpm.
7. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 1; It is characterized in that; The described shearing process using of step (2) following steps: through torque rheometer flat sheet membranes is heated to 125～145 ℃ of shear temperature, the control shear rate is 10～50s
-1, strain amplitude is 20～100%, obtains being orientated flat sheet membranes.
8. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 1; It is characterized in that; The described drawing process of step (2) adopts following steps: through the controlled universal electrical puller system of draft temperature with the flat sheet membranes stretch orientation; Draft temperature is 40～100 ℃, and rate of extension is 50～100mm/min, and elongation strain is 100～300%.
9. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 1 is characterized in that, the described extractant of step (3) is selected from the one or more combination in absolute ethyl alcohol, glycerine, n-butanol or the chloroform.
10. the preparation method of a kind of ultra-high molecular weight polyethylene micro-filtration membrane according to claim 1 is characterized in that, the described drying of step (4) is 80 ℃ with the baking temperature of annealing typing, and be 3h drying time, and annealing temperature is 110 ℃, and annealing time is 10h.
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