CN101781417A - Method for preparing polyolefin microporous membrane through wet process - Google Patents
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 25
- 239000004700 high-density polyethylene Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 15
- 229920001903 high density polyethylene Polymers 0.000 claims description 12
- 238000009998 heat setting Methods 0.000 claims description 10
- 229920005672 polyolefin resin Polymers 0.000 claims description 10
- 230000002457 bidirectional effect Effects 0.000 claims description 9
- 230000001360 synchronised effect Effects 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 229920013716 polyethylene resin Polymers 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 238000009997 thermal pre-treatment Methods 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000001816 cooling Methods 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 9
- 238000002137 ultrasound extraction Methods 0.000 description 9
- 238000007654 immersion Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Abstract
The invention discloses a method for preparing polyolefin microporous membrane through wet process, aiming at solving the problems of low mechanical strength and poor uniformity of the clearances of the membrane. The method takes polyolefine resin, nucleating agent and solvent as the materials to prepare polyolefin microporous membrane through polyolefine solution preparation procedure, extrusion and gel sheet forming procedure, drawing procedure, membrane forming and solvent removal procedure, drying procedure and heat treatment stereotyping procedure. The preparation technique is simple and the polyolefin microporous membrane prepared through the method can be used as medical dressing, clothes lining, various separation membranes, water treatment membrane as well as membranes for a super capacitor, a battery and the like.
Description
Technical field
The invention belongs to the method for the preparing polyolefin microporous membrane through wet process in the technical field of macromolecules.
Background technology
Microporous polyolefin film is polymeric membrane and the aperture porous-film between 5nm～1000nm, and the individual layer microporous polyolefin film has been widely used in preparing capacitor diaphragm, battery diaphragm and various separatory membrane.In known technology, existing method for preparing polyolefin microporous membrane comprises fusion drawn method (being commonly called as dry method) and thermally induced phase separation (being commonly called as wet method), thermally induced phase separation is at high temperature polymkeric substance to be dissolved in high boiling point, in the solvent of low volatility, form homogeneous phase solution, cooling cooling then, system is sent out the dirt phase-splitting in the process of cooling, formation is external phase with the polymkeric substance, solvent is two structures of disperse phase, select for use suitable volatile reagent that solvent cleaning is fallen again, thereby the polymer microporous film that acquisition has certain structural shape, be mainly used in the polyethylene battery diaphragm of preparation individual layer at present, seriously there are residual problem in used a large amount of solvents of the poor mechanical property of prepared microporous membrane, especially film forming and washing composition, make film forming ventilation property and reduce, made microporous membrane hole homogeneity is relatively poor.
Summary of the invention
The purpose of this invention is to provide that a kind of preparation technology is simple, the raw material mixing uniformity is good, solvent and washing composition be residual low, the method for a kind of new preparing polyolefin microporous membrane through wet process of gained microporous polyolefin film product strength height, good permeability, microporous membrane porous nickel.
Addressing the above problem the technical scheme that is adopted is:
A kind of method of preparing polyolefin microporous membrane through wet process, it is a raw material with polyolefin resin, nucleator, solvent, adopts the thermic phase disengagement method to prepare microporous membrane, and is undertaken by following operation:
The preparation process of A, polyolefin solution
Earlier become blend (adding the nucleator purpose in raw material is the formation that prevents big spherocrystal) with the polyolefin resin in the raw material and nucleator are mixing in mixing roll, treat mixing evenly after, directly join in the screw extrusion press, add solvent simultaneously, under 160～260 ℃ of temperature condition, polymeric blends is dissolved in and is made for polyolefin solution in the solvent through screw extrusion press;
B, extrude and the formation operation of gel sheet
The homogeneous phase polyolefin solution that above-mentioned A operation screw extrusion press die head is extruded attaches to by static tag or air knife tag on 20～40 ℃ the chilling roller, is cooled to gel sheet;
C, stretching process
The gel sheet that the B operation is made after thermal pretreatment, is carried out synchronous bidirectional stretching film forming earlier again under 60～135 ℃, stretching ratio is 3 * 3～7 * 7 times, and pulling speed is 1～15 meter/minute;
The removal operation of D, film forming solvent
With the film that the C operation is drawn into, in clean-out system, soak 1～5 minute after, under the ultrasonic wave effect, remove film forming solvent through ultrasonic generator, used frequency of ultrasonic scope is 20～500kHz, intensity is 1～15W/cm
2, all cleaning process is carried out under room temperature, normal pressure;
This operation adopts the ultrasonic extraction technology fast, efficiently.Ultrasonic extraction mainly is to act on clean-out system by the quick mechanical vibration wave that PZT (piezoelectric transducer) produces, clean-out system with certain vibrational energy acts on and contains the sample matrices that target is cleaned thing, thereby reducing target cleans reactive force between thing and the sample matrices and realizes solid～liquid extracting and separating, hyperacoustic vibration is even, the reactive force unanimity that each point is subjected in the sample, entire sample removal of solvents good uniformity.
E, drying process
Behind D operation removal film forming solvent, be provided with the pneumatic conveying dryer of man type chute's line rubber rollers in entering into, remove impurity and the surperficial clean-out system that attaches thereof that film is separated out, and the dry film that flattens, the air that pneumatic conveying dryer is blown into is preheating to 30～80 ℃ earlier, and the drying treatment process vertically keeps tension force, laterally is under the lax state and carries out at film;
F, thermal treatment shaping process
Microporous membrane after the E operation under 60～140 ℃ of conditions, is carried out heat setting type and handles, and shaping time is 0.5～5.0 minute, makes the microporous polyolefin film product.
The method of above-mentioned preparing polyolefin microporous membrane through wet process, used polyolefin resin are that weight-average molecular weight is 2 * 10
5～5 * 10
5High-density polyethylene resin and weight-average molecular weight be 2 * 10
5～8 * 10
5Acrylic resin any.
The method of above-mentioned preparing polyolefin microporous membrane through wet process, described polyolefin resin are that weight-average molecular weight is 2 * 10
5～5 * 10
5High-density polyethylene resin and weight-average molecular weight be 1 * 10
6～5 * 10
6The mixture of polyvinyl resin with super-high molecular weight, wherein the content of ultrahigh molecular weight polyethylene(UHMWPE) accounts for 10～50% of total amount by weight, the best is 15～30%.
The method of above-mentioned preparing polyolefin microporous membrane through wet process, described polyolefin resin is the mixture of high-density polyethylene resin and polyvinyl resin with super-high molecular weight, employing order feeding mode in the mixing process of the preparation process of polyolefin solution, promptly under 230～260 ℃, polyvinyl resin with super-high molecular weight is added in the mixing roll earlier mixing, it is cooled to 150～200 ℃ then, adding high-density polyethylene resin and nucleator again continues mixing, treat mixing evenly after, join screw extrusion press continuously, the polymeric blends continuous-dissolution becomes polyolefin solution under 160～260 ℃ of temperature condition in screw extrusion press in solvent.In ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) mixed system, add nucleator and can accelerate nucleus formation speed, make the crystal grain of formation tiny and even, also help the formation of two kinds of polymkeric substance eutectics simultaneously, thereby significantly improve the physicals of matrix material.
The method of above-mentioned preparing polyolefin microporous membrane through wet process, described nucleator be in phenylformic acid, stearate, the talcum powder wantonly a kind to the mixture of 2～3 kinds of any proportionings wherein, the content of nucleator is 0.8～2.0% of polyolefin blend total amount by weight.
The method of above-mentioned preparing polyolefin microporous membrane through wet process, described film forming solvent for use are that boiling point is higher than 270 ℃, and the best is to be higher than any of 300 ℃ whiteruss and mineral oil, and the consumption of solvent is 70～90% of polyolefine and membrane-forming agent total amount by weight.
The method of above-mentioned preparing polyolefin microporous membrane through wet process, used washing composition is the washed with dichloromethane agent in the removal operation of described film forming solvent, also can select in other the hydro carbons, hydrochloric ether, hydrofluoric ether any for use.
When the present invention produces preparation, by the design technology requirement, install equipment used mixing roll, screw extrusion press, two-way stretch equipment, ultrasonic generator, be provided with the pneumatic conveying dryer of man type chute's line rubber rollers etc., be ready to starting material and washing composition etc.Produce preparation microporous polyolefin film product according to the described operation of preparation method of the present invention.
It is low that the present invention has solved the prepared microporous polyolefin film product of existing method for preparing polyolefin microporous membrane mechanical strength effectively, the problem that the membrane pores homogeneity is relatively poor.Show that through testing result on trial for several times the raw material mixing uniformity is good, solvent and washing composition are residual low, prepared microporous polyolefin film product strength height, good permeability, advantages such as microporous membrane porous nickel.Be applicable to the preparation microporous polyolefin film, gained microporous polyolefin film product is suitable for makes medical dressing, clothes lining, various separatory membrane, membrane for water treatment and ultracapacitor and battery diaphragm etc.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
A is 3.5 * 10 250 ℃ of weight-average molecular weight that will account for polyolefine total amount 20% down
6Polyvinyl resin with super-high molecular weight (125Kg) add in the mixing roll mixingly, it is cooled to 180 ℃ then, adding the weight-average molecular weight that accounts for polyolefine total amount 80% again is 3.5 * 10
5High density polyethylene(HDPE) (500Kg) and account for the nucleator Zinic stearas (ZnSt of polyolefine total amount 0.8%
2) (5Kg), the preparation polyolefin blend;
Polyolefin blend that the b handle obtains and whiteruss add twin screw extruder in 1: 4 ratio, extrude by T pattern head under 215 ℃, and cooling roller is cooled to gel sheet, and chill-roll temperature is 35 ℃;
C stretches 5 * 5 times at 115 ℃ of following synchronous bidirectionals to the gel sheet material that obtains;
In the dichloromethane solution of film immersion under room temperature, normal pressure after d will stretch, adopt ultrasonic extraction, ultrasonic frequency is 20kHz, and intensity is 1.5W/cm
2, washing time is 1 minute, and is air-dry after groove line rubber rollers;
F is made for the polyethene microporous membrane product 120 ℃ of following heat setting types 3 minutes.Product performance see Table 1
Embodiment 2
A is 3.5 * 10 250 ℃ of weight-average molecular weight that will account for polyolefine total amount 20% down
6Polyvinyl resin with super-high molecular weight (125Kg) add in the mixing roll mixingly, it is cooled to 180 ℃ then, adding the weight-average molecular weight that accounts for polyolefine total amount 80% again is 3.5 * 10
5High density polyethylene(HDPE) (500Kg) and account for the nucleator Zinic stearas (ZnSt of polyolefine total amount 1.2%
2) (7.5Kg), the preparation polyolefin blend;
Polyolefin blend that the b handle obtains and whiteruss (2000Kg) add twin screw extruder in 1: 4 ratio, extrude by T pattern head under 215 ℃, and cooling roller is cooled to gel sheet, and chill-roll temperature is 35 ℃;
C stretches 5 * 5 times at 115 ℃ of following synchronous bidirectionals to the gel sheet material that obtains;
In the dichloromethane solution of film immersion under room temperature, normal pressure after d will stretch, adopt ultrasonic extraction, ultrasonic frequency is 20kHz, and intensity is 1.5W/cm
2, washing time is 1 minute, and is air-dry after groove line rubber rollers;
F is made for the polyethene microporous membrane product 120 ℃ of following heat setting types 3 minutes.Product performance see Table 1
Embodiment 3
A is 3.5 * 10 250 ℃ of weight-average molecular weight that will account for polyolefine total amount 20% down
6Polyvinyl resin with super-high molecular weight (125Kg) add in the mixing roll mixingly, it is cooled to 180 ℃ then, adding the weight-average molecular weight that accounts for polyolefine total amount 80% again is 3.5 * 10
5High density polyethylene(HDPE) (500Kg) and account for the nucleator Zinic stearas (ZnSt of polyolefine total amount 0.8%
2) (5Kg), the preparation polyolefin blend;
Polyolefin blend that the b handle obtains and whiteruss (2000Kg) add twin screw extruder in 1: 4 ratio, extrude by T pattern head under 215 ℃, and cooling roller is cooled to gel sheet, and chill-roll temperature is 35 ℃;
C stretches 5 * 5 times at 115 ℃ of following synchronous bidirectionals to the gel sheet material that obtains;
In the dichloromethane solution of film immersion under room temperature, normal pressure after d will stretch, adopt ultrasonic extraction, ultrasonic frequency is 50kHz, and intensity is 1.5W/cm
2, washing time is 1 minute, and is air-dry after groove line rubber rollers;
F is made for the polyethene microporous membrane product 120 ℃ of following heat setting types 3 minutes.Product performance see Table 1
Embodiment 4
A is 3.5 * 10 250 ℃ of weight-average molecular weight that will account for polyolefine total amount 20% down
6Polyvinyl resin with super-high molecular weight (125Kg) add in the mixing roll mixingly, it is cooled to 180 ℃ then, adding the weight-average molecular weight that accounts for polyolefine total amount 80% again is 3.5 * 10
5High density polyethylene(HDPE) (500Kg) and account for the nucleator Zinic stearas (ZnSt of polyolefine total amount 0.8%
2) (5Kg), the preparation polyolefin blend;
Polyolefin blend that the b handle obtains and whiteruss (2000Kg) add twin screw extruder in 1: 4 ratio, extrude by T pattern head under 215 ℃, and cooling roller is cooled to gel sheet, and chill-roll temperature is 35 ℃;
C stretches 5 * 5 times at 115 ℃ of following synchronous bidirectionals to the gel sheet material that obtains;
In the dichloromethane solution of film immersion under room temperature, normal pressure after d will stretch, adopt ultrasonic extraction, ultrasonic frequency is 100kHz, and intensity is 1.5W/cm
2, washing time is 1 minute, and is air-dry after groove line rubber rollers;
F is made for the polyethene microporous membrane product 120 ℃ of following heat setting types 3 minutes.Product performance see Table 1
Embodiment 5
The weight-average molecular weight that a will account for polyolefine total amount 20% is 3.5 * 10
6Polyvinyl resin with super-high molecular weight (125Kg) and the weight-average molecular weight that accounts for polyolefine total amount 80% be 3.5 * 10
5High-density polyethylene resin (500Kg) and account for the nucleator Zinic stearas (ZnSt of polyolefine total amount 0.8%
2) (5Kg) mixing under 215 ℃, the preparation polyolefin blend;
Polyolefin blend that the b handle obtains and whiteruss (2000Kg) add twin screw extruder in 1: 4 ratio, extrude by T pattern head under 215 ℃, and cooling roller is cooled to gel sheet, and chill-roll temperature is 35 ℃;
C stretches 5 * 5 times at 115 ℃ of following synchronous bidirectionals to the gel sheet material that obtains;
In the hexane solution of film immersion under room temperature, normal pressure after d will stretch, adopt ultrasonic extraction, ultrasonic frequency is 50kHz, and intensity is 1.5W/cm
2, washing time is 1 minute, and is air-dry after groove line rubber rollers;
F is made for the polyethene microporous membrane product 120 ℃ of following heat setting types 3 minutes.Product performance see Table 1
Embodiment 6
A is 3.5 * 10 250 ℃ of weight-average molecular weight that will account for polyolefine total amount 20% down
6Polyvinyl resin with super-high molecular weight (125Kg) add in the mixing roll mixingly, it is cooled to 180 ℃ then, adding the weight-average molecular weight that accounts for polyolefine total amount 80% again is 3.5 * 10
5High density polyethylene(HDPE) (500Kg), the preparation polyolefin blend;
Polyolefin blend that the b handle obtains and whiteruss (2000Kg) add twin screw extruder in 1: 4 ratio, extrude by T pattern head under 215 ℃, and cooling roller is cooled to gel sheet, and chill-roll temperature is 35 ℃;
C stretches 5 * 5 times at 115 ℃ of following synchronous bidirectionals to the gel sheet material that obtains;
In the dichloromethane solution of film immersion under room temperature, normal pressure after d will stretch, adopt ultrasonic extraction, ultrasonic frequency is 50kHz, and intensity is 1.5W/cm
2, washing time is 1 minute, and is air-dry after groove line rubber rollers;
F is made for the polyethene microporous membrane product 120 ℃ of following heat setting types 3 minutes.Product performance see Table 1
Embodiment 7
A is 3.5 * 10 250 ℃ of weight-average molecular weight that will account for polyolefine total amount 20% down
6Polyvinyl resin with super-high molecular weight (125Kg) add in the mixing roll mixingly, it is cooled to 180 ℃ then, adding the weight-average molecular weight that accounts for polyolefine total amount 80% again is 3.5 * 10
5High density polyethylene(HDPE) (500Kg) and account for the nucleator Zinic stearas (ZnSt of polyolefine total amount 0.8%
2) (5Kg), the preparation polyolefin blend;
Polyolefin blend that the b handle obtains and whiteruss (2000Kg) add twin screw extruder in 1: 4 ratio, extrude by T pattern head under 215 ℃, and cooling roller is cooled to gel sheet, and chill-roll temperature is 35 ℃;
C stretches 5 * 5 times at 115 ℃ of following synchronous bidirectionals to the gel sheet material that obtains;
Wash in the dichloromethane solution of film immersion under room temperature, normal pressure after d will stretch, washing time is 1 minute, and is air-dry after groove line rubber rollers;
F is made for the polyethene microporous membrane product 120 ℃ of following heat setting types 3 minutes.Product performance see Table 1
Embodiment 8
A is 2.5 * 10 with weight-average molecular weight
5Acrylic resin (500Kg) and whiteruss (2000Kg) add twin screw extruder in 1: 4 ratio;
B extrudes by T pattern head under 215 ℃, and cooling roller is cooled to gel sheet, and chill-roll temperature is 35 ℃;
C stretches 5 * 5 times down at 125 ℃ to the gel sheet material that obtains;
In the dichloromethane solution of film immersion under room temperature, normal pressure after d will stretch, adopt ultrasonic extraction, ultrasonic frequency is 20kHz, and intensity is 1.5W/cm
2, washing time is 1 minute, and is air-dry after groove line rubber rollers;
E makes the microporous polyolefin film product 120 ℃ of following heat setting types 3 minutes.Product performance see Table 1
Table 1
TD represents that transverse tensile strength, MD are longitudinal tensile strength in the table.Embodiment the 1,2, the 6th in the last table, and the research nucleator is respectively interpolation 0.8%, 1.2%, reaches three kinds of situations of not adding nucleator the influence of membrane properties;
Embodiment the 2,3,4, the 7th in the last table, and the research ultrasonic wave is to the influence of washing effect, and ultrasonic frequency is made as 20kHz, 50kHz, 100kHz respectively and does not have several situations of ultrasonic wave;
Embodiment 5 does not feed intake in certain sequence in the last table, is used for comparing with the barrier film of the preparation that feeds intake in certain sequence; The raw material that embodiment 8 uses in the last table is a polypropylene.
Tensile strength: measure according to ASTM D882.
The testing method of puncture intensity: measuring with front end is that the diameter of sphere (radius-of-curvature is R=0.5mm) is the pin of 1mm, the maximum load when penetrating polyethene microporous membrane with the speed of 2mm/ second.
Ventilation property: adopt densometer, 100cm under 12.2 inch of water
3Air is by 1 square inch of product required time.
Claims (7)
1. the method for a preparing polyolefin microporous membrane through wet process is characterized in that, it is a raw material with polyolefin resin, nucleator, solvent, adopts the thermic phase disengagement method to prepare microporous membrane, and is undertaken by following operation:
The preparation process of A, polyolefin solution
Earlier with the polyolefin resin in the raw material and nucleator in mixing roll 150～260 ℃ mixingly down become blend, treat mixing evenly after, directly join in the screw extrusion press, add solvent simultaneously, under 160～260 ℃ of temperature condition, polymeric blends is dissolved in and makes polyolefin solution in the solvent through screw extrusion press;
B, extrude and gel sheet forms operation
The homogeneous phase polyolefin solution that screw extrusion press die head in the above-mentioned A operation is extruded attaches to by the static tag on 20～40 ℃ the chilling roller, is cooled to gel sheet;
C, stretching process
The gel sheet that the B operation is made after thermal pretreatment, is carried out synchronous bidirectional stretching film forming earlier again under 60～135 ℃, stretching ratio is 3 * 3～7 * 7 times, and pulling speed is 1～15 meter/minute;
D, film forming solvent are removed operation
With the film that the C operation is drawn into, in clean-out system, soak 1～5 minute after, under the ultrasonic wave effect, remove film forming solvent through ultrasonic generator, used frequency of ultrasonic scope is 20～500kHz, intensity is 1～15W/cm
2, all cleaning process is carried out under room temperature, normal pressure;
E, drying process
After the D operation is removed film forming solvent, be provided with the pneumatic conveying dryer of man type chute's line rubber rollers in entering into, remove impurity and the surperficial clean-out system that attaches thereof that film is separated out, and the dry film that flattens, the air that pneumatic conveying dryer is blown into is preheating to 30～80 ℃ earlier, and the drying treatment process vertically keeps tension force, laterally is under the lax state and carries out at film;
F, thermal treatment shaping process
Microporous membrane after the E operation under 60～140 ℃ of conditions, is carried out heat setting type and handles, and shaping time is 0.5～5.0 minute, makes the microporous polyolefin film product.
2. the method for preparing polyolefin microporous membrane through wet process according to claim 1 is characterized in that, described polyolefin resin is that weight-average molecular weight is 2 * 10
5～5 * 10
5High-density polyethylene resin or weight-average molecular weight be 2 * 10
5～8 * 10
5Acrylic resin a kind of.
3. the method for preparing polyolefin microporous membrane through wet process according to claim 1 is characterized in that, described polyolefin resin is that weight-average molecular weight is 2 * 10
5～5 * 10
5High-density polyethylene resin and weight-average molecular weight be 1 * 10
6～5 * 10
6The mixture of polyvinyl resin with super-high molecular weight, wherein the content of ultrahigh molecular weight polyethylene(UHMWPE) accounts for 10～50% of total amount by weight.
4. the method for preparing polyolefin microporous membrane through wet process according to claim 3, it is characterized in that, when polyolefin resin is selected the mixture of polyvinyl resin with super-high molecular weight and high-density polyethylene resin for use, the mode that employing feeds intake in proper order in the mixing process, promptly under 230～260 ℃, polyvinyl resin with super-high molecular weight is added in the mixing roll earlier mixing, it is cooled to 150～200 ℃ then, adding high-density polyethylene resin and nucleator again continues mixing, treat mixing evenly after, join screw extrusion press continuously, in screw extrusion press, under 160～260 ℃ of temperature condition the polymeric blends continuous-dissolution is made polyolefin solution in solvent.
5. the method for preparing polyolefin microporous membrane through wet process according to claim 4, it is characterized in that, described nucleator is a kind of or its mixture in phenylformic acid, stearate or the talcum powder, and the content of nucleator is 0.8～2.0% of polyolefin blend total amount by weight.
6. the method for preparing polyolefin microporous membrane through wet process according to claim 5, it is characterized in that, described film forming solvent is that boiling point is higher than any of 270 ℃ whiteruss or mineral oil, and the consumption of solvent is 70～90% of polyolefine and membrane-forming agent total amount by weight.
7. the method for preparing polyolefin microporous membrane through wet process according to claim 6 is characterized in that, removing used washing composition in the operation at film forming solvent is a kind of in hydro carbons, hydrochloric ether or the hydrofluoric ether.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010107865XA CN101781417B (en) | 2010-02-10 | 2010-02-10 | Method for preparing polyolefin microporous membrane through wet process |
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Cited By (10)
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| CN102064299A (en) * | 2010-12-25 | 2011-05-18 | 佛山塑料集团股份有限公司 | Polyolefin multi-layer porous diaphragm for lithium ion battery and preparation method thereof |
| CN102148346A (en) * | 2011-03-11 | 2011-08-10 | 河南义腾新能源科技有限公司 | Polyolefin microporous diaphragm and preparation method thereof |
| CN103342842A (en) * | 2013-07-18 | 2013-10-09 | 中国石油化工股份有限公司 | High-density polyethylene resin composition for microporous membrane and preparation method of high-density polyethylene resin composition |
| CN103762327A (en) * | 2014-01-17 | 2014-04-30 | 苏州鼎机新能源材料科技有限公司 | Lithium ion battery separator and production technology thereof |
| CN104292574A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Polyethylene composition used for lithium ion battery separator and preparation method thereof |
| CN105330937A (en) * | 2015-11-17 | 2016-02-17 | 梅庆波 | Method for wet preparation of PE (polyethylene) plastic polymers |
| CN107938007A (en) * | 2018-01-03 | 2018-04-20 | 江苏金由新材料有限公司 | The system and method for PTFE staple fibers is prepared using different molecular weight material |
| US10569230B2 (en) | 2015-05-30 | 2020-02-25 | Core Energy Recovery Solutions Inc. | Supported water vapor transport membrane comprising polyethylene oxide copolymer |
| CN113893710A (en) * | 2021-11-16 | 2022-01-07 | 无锡恩捷新材料科技有限公司 | High-flux polyethylene water treatment membrane and preparation method thereof |
| CN115160697A (en) * | 2022-08-16 | 2022-10-11 | 温州鑫泰新材料股份有限公司 | Puncture-resistant PP (polypropylene) film for lithium battery and preparation method thereof |
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| CN102148346A (en) * | 2011-03-11 | 2011-08-10 | 河南义腾新能源科技有限公司 | Polyolefin microporous diaphragm and preparation method thereof |
| CN102148346B (en) * | 2011-03-11 | 2013-04-24 | 河南义腾新能源科技有限公司 | Polyolefin microporous diaphragm and preparation method thereof |
| CN103342842A (en) * | 2013-07-18 | 2013-10-09 | 中国石油化工股份有限公司 | High-density polyethylene resin composition for microporous membrane and preparation method of high-density polyethylene resin composition |
| CN104292574B (en) * | 2013-07-18 | 2016-08-10 | 中国石油化工股份有限公司 | Lithium ion battery separator polyethylene composition and preparation method thereof |
| CN104292574A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Polyethylene composition used for lithium ion battery separator and preparation method thereof |
| CN103342842B (en) * | 2013-07-18 | 2015-07-08 | 中国石油化工股份有限公司 | High-density polyethylene resin composition for microporous membrane and preparation method of high-density polyethylene resin composition |
| CN103762327B (en) * | 2014-01-17 | 2016-07-27 | 苏州鼎机新能源材料科技有限公司 | A kind of lithium ion battery separator and production technology thereof |
| CN103762327A (en) * | 2014-01-17 | 2014-04-30 | 苏州鼎机新能源材料科技有限公司 | Lithium ion battery separator and production technology thereof |
| US10569230B2 (en) | 2015-05-30 | 2020-02-25 | Core Energy Recovery Solutions Inc. | Supported water vapor transport membrane comprising polyethylene oxide copolymer |
| CN105330937A (en) * | 2015-11-17 | 2016-02-17 | 梅庆波 | Method for wet preparation of PE (polyethylene) plastic polymers |
| CN107938007A (en) * | 2018-01-03 | 2018-04-20 | 江苏金由新材料有限公司 | The system and method for PTFE staple fibers is prepared using different molecular weight material |
| CN113893710A (en) * | 2021-11-16 | 2022-01-07 | 无锡恩捷新材料科技有限公司 | High-flux polyethylene water treatment membrane and preparation method thereof |
| WO2023087617A1 (en) * | 2021-11-16 | 2023-05-25 | 无锡恩捷新材料科技有限公司 | High-flux polyethylene water treatment membrane and preparation method therefor |
| CN113893710B (en) * | 2021-11-16 | 2024-04-12 | 无锡恩捷新材料科技有限公司 | High-flux polyethylene water treatment membrane and preparation method thereof |
| CN115160697A (en) * | 2022-08-16 | 2022-10-11 | 温州鑫泰新材料股份有限公司 | Puncture-resistant PP (polypropylene) film for lithium battery and preparation method thereof |
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