CN103921449B - Ultrathin high-strength polyolefin microporous film and preparation method thereof - Google Patents
Ultrathin high-strength polyolefin microporous film and preparation method thereof Download PDFInfo
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000008961 swelling Effects 0.000 claims abstract description 23
- 238000005266 casting Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000003085 diluting agent Substances 0.000 claims description 33
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- -1 octadecyl pentaerythrite Chemical compound 0.000 claims description 14
- 230000004888 barrier function Effects 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000005662 Paraffin oil Substances 0.000 claims description 7
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 150000004291 polyenes Chemical class 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 238000000048 melt cooling Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 5
- 229920005672 polyolefin resin Polymers 0.000 abstract description 2
- 238000002145 thermally induced phase separation Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 description 5
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 3
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a preparation method of an ultrathin high-strength polyolefin microporous film. Polyolefin resin is used as a raw material, and the polyolefin microporous film is prepared by a thermally induced phase separation principle. The method comprises the following steps: a. polyolefin swelling dissolving; b. sheet casting; c. stretching a polyolefin cast film once; and d. stretching the polyolefin cast film secondarily. The invention also discloses the polyolefin microporous film prepared by the method. The method has the advantages of semi-continuous production convenience, simple process flow and simplicity in operation.
Description
Technical field
The present invention relates to lithium rechargeable battery, especially relate to one kind and semi-successive cultivation, technological process can be facilitated simple
The preparation method of easy-operating ultra-thin high-strength MIcroporous polyolefin film and MIcroporous polyolefin film.
Background technology
Because polyolefin has good chemical stability and superior physical properties, its microporous barrier barrier film is widely used in electricity
Pond, capacitor, water process, water desalination and bio-medical and the field such as medical, are especially used as the barrier film of lithium ion battery in a large number.
In the prior art, the method preparing MIcroporous polyolefin film has dry process (simple tension and biaxial tension) and wet processing
(thermally induced phase separation).With the contrast of other methods, wet processing can produce thinner microporous barrier, and its thickness is uniformly, physics
Excellent performance.
The physical property of perforated membrane can be improved using the resin of HMW in barrier film processing technology.But vistanex
Strand long and be nonpolar crystalline state polymer, melting the heating period, due to the effect of high temperature and Strong shear, gather
The easily hot oxygen of olefin hydrocarbon molecules chain, mechanical degradation, make the chemical bond rupture of strand become active free radical and hydroperoxides, and hydrogen
Peroxide decomposes generation hydrocarbon oxygen radical and hydroxyl radical free radical further, leads to a series of free chain reaction to cause poly-
There is basic change in the structure of olefin resin and property.Meanwhile, in the extrusion Solid Conveying and Melting stage, because shearing high temperature action, polyene
The easy carbonization of hydrocarbon resin, the fine particle after its carbonization in slab can with melt extrusion, finally make to occur on film fisheye or
Other bad problems, cause product quality problem, reduce yield rate.In addition, resin carbon compound also easily accumulates in twin-screw squeezing
Go out in machine, need dismantling screw to remove, can cause, to producing tremendous influence, undoubtedly can greatly increase processing cost, waste
The valuable production time, reduce production efficiency.
Content of the invention
For overcoming disadvantages mentioned above, provide and a kind of can facilitate simple to operation ultra-thin high-strength of semi-successive cultivation, technological process
The preparation method of MIcroporous polyolefin film.
The purpose of the present invention is achieved through the following technical measures, a kind of preparation side of ultra-thin high-strength MIcroporous polyolefin film
Method, it is prepared polyolefin porous membrane using Thermal inactive principle, comprises the steps with vistanex as raw material：
A. the swelling dissolving of polyolefin：Antioxidant is dissolved in diluent kneader, adds polyene into diluent
Hydrocarbon resin powder is stirred uniformly, and under nitrogen protection, it is swelling to be warming up to 80 DEG C -150 DEG C insulations, obtains swelling polyolefin；
Under nitrogen protection, add diluent in swelling polyolefin, dissolving at 100-400 DEG C forms mixture；
B. slab：The mixture of previous step gained is sent into extruder by gear-conveying pump, mixed using extruder plasticizing
Compound forms polyolefin solution, and the polyolefin solution obtaining is extruded from die head under the control of measuring pump, obtains polyolefin melt；
C. polyolefin casting films one-off drawing：Melt cooling, after die head extrusion, is become by polyolefin melt by chilling roller
Obtain diaphragm, then pass through biaxial orientation stretching machine and carry out biaxial tension, then utilize diluent to extract oil removing to diaphragm at room temperature
And be dried；
D. polyolefin film succeeding stretch：Diaphragm after extraction is carried out succeeding stretch or succeeding stretch in hot-stretch case again
MIcroporous polyolefin film is obtained after processing with postorder.
As a kind of mode of priority, in the swelling dissolving step of described polyolefin, in obtained mixture vistanex with
Diluent weight is than for 1:1-10.
As a kind of mode of priority, described extruder is screw extruder, and the screw speed of described screw extruder is 50-
250rpm, the operating temperature of extruder is 100-400 DEG C, and output pressure is 10-50MPa；Chilling roller operating temperature is 5-50 DEG C；
Casting films biaxial tension multiplying power is 1-10 × 2-20.
As a kind of mode of priority, described antioxidant is hindered phenol, phosphite ester or organic sulfur compound, described antioxidant with
The part by weight of vistanex is 1:50-10000.
As a kind of mode of priority, described antioxidant is 3- (3,5- di-t-butyl -4- hydroxy benzenes) propionic acid stearyl,
The double lauryl alcohol ester or thio two of phosphorous acid dodecyl three ester, distearyl pentaerythritol diphosphite, thio-2 acid
Double isomerous tridecanol ester of propionic acid etc..
As a kind of mode of priority, described diluent is one or more of decahydronaphthalene, kerosene, paraffin oil, paraffin.
As a kind of mode of priority, described diluent is paraffin oil or paraffin.
As a kind of mode of priority, the mean molecule quantity of described vistanex is 1 × 104～1 × 107.Preferably 1 × 104
～5 × 106, it is more highly preferred to 5 × 105～5 × 106.
As a kind of mode of priority, the particle size range of described polyolefin powder is 0.01 μm -10 μm.Preferably 0.1 μm -2 μm.
The invention also discloses a kind of MIcroporous polyolefin film prepared by above-mentioned preparation method, the thickness of MIcroporous polyolefin film
For 5-30 μm, porosity is 32-55%, and average pore size is 25-55 nanometer, and when 105 DEG C, percent thermal shrinkage is no more than 4.0, MD
Tensile strength is more than 160MPa, and TD tensile strength is more than 150MPa, and air penetrability is more than 180 ± 50sec/100m.
The invention has the advantages that：
The present invention prepares polyolefin/diluent homogeneous phase solution using pre-swollen dissolution method, can be in low temperature, low sheraing speed
Realize the plasticizing of high molecular polyolefine and diluent under the conditions of degree etc. and mix, high-quality MIcroporous polyolefin film can be obtained.
The present invention adopt the antioxidant containing carbochain, can uniformly mix with diluent and adopt same extractant by its
Extraction is clean, both ensure that the antioxidation to polymer melt, and has not affected product quality.
The present invention is that a kind of have high efficiency and excellent extrusion mixing and draftability prepares the side of microporous barrier
Method.
The present invention have can semi-successive cultivation, technological process simple to operation；The micropore film thickness of present invention preparation is 5
～30 μm of barrier film, porosity is 32～55%, and average pore size is 25～55 nanometers, and when 105 DEG C, percent thermal shrinkage is to be not more than
4.0, MD tensile strengths are more than 160MPa, and TD tensile strength is more than 150MPa.
Brief description
Fig. 1 is the ESEM micro-structure diagram of the MIcroporous polyolefin film of the embodiment of the present invention 1.
Specific embodiment
With reference to embodiment and compare accompanying drawing the present invention is described in further detail.
A kind of preparation method of ultra-thin high-strength MIcroporous polyolefin film, it is divided with vistanex as raw material using thermic phase
Prepare polyolefin porous membrane from principle, comprise the steps：
A. the swelling dissolving of polyolefin：Antioxidant is dissolved in diluent kneader, adds polyene into diluent
Hydrocarbon resin powder is stirred uniformly, and under nitrogen protection, it is swelling to be warming up to 80 DEG C -150 DEG C insulations, obtains swelling polyolefin；
Under nitrogen protection, add diluent in swelling polyolefin, dissolving at 100-400 DEG C forms mixture；
B. slab：The mixture of previous step gained is sent into extruder by gear-conveying pump, mixed using extruder plasticizing
Compound forms polyolefin solution, and the polyolefin solution obtaining is extruded from die head under the control of measuring pump, obtains polyolefin melt；
C. polyolefin casting films one-off drawing：Melt cooling, after die head extrusion, is become by polyolefin melt by chilling roller
Obtain diaphragm, then pass through biaxial orientation stretching machine and carry out biaxial tension, then utilize diluent to extract oil removing to diaphragm at room temperature
And be dried；
D. polyolefin film succeeding stretch：Diaphragm after extraction is carried out succeeding stretch or succeeding stretch in hot-stretch case again
MIcroporous polyolefin film is obtained after processing with postorder.
Thickness using the MIcroporous polyolefin film prepared by said method is 5-30 μm, and porosity is 32-55%, average hole
Footpath is 25-55 nanometer, and when 105 DEG C, percent thermal shrinkage is that no more than 4.0, MD tensile strength is more than 160MPa, and TD tensile strength is big
In 150MP, air penetrability is more than 180 ± 50sec/100m.
The preparation method of the ultra-thin high-strength MIcroporous polyolefin film of the present invention, on the basis of previous technique scheme, specifically
It is in the swelling dissolving step of polyolefin, in obtained mixture, vistanex and diluent weight are than for 1:1-10.
The preparation method of the ultra-thin high-strength MIcroporous polyolefin film of the present invention, on the basis of previous technique scheme, specifically
Be extruder be screw extruder, the screw speed of screw extruder is 50-250rpm, and the operating temperature of extruder is 100-
400 DEG C, output pressure is 10-50MPa；Chilling roller operating temperature is 5-50 DEG C；Casting films biaxial tension multiplying power is 1-10 × 2-
20.
The preparation method of the ultra-thin high-strength MIcroporous polyolefin film of the present invention, on the basis of previous technique scheme, specifically
Be antioxidant be hindered phenol, phosphite ester or organic sulfur compound, described antioxidant is 1 with the part by weight of vistanex:50-
10000.Preferably select the antioxidant containing long-chain carbon structure, more preferably select the antioxidant of more than C12 backbone, bag
Include but be not limited to 3- (3,5- di-t-butyl -4- hydroxy benzenes) propionic acid stearyl, phosphorous acid dodecyl three ester, double 18
Alkyl pentaerythritol bis-phosphite, the double lauryl alcohol ester of thio-2 acid, double isomerous tridecanol ester of thio-2 acid etc..
The preparation method of the ultra-thin high-strength MIcroporous polyolefin film of the present invention, on the basis of previous technique scheme, specifically
Be diluent be decahydronaphthalene, one or more of kerosene, paraffin oil, paraffin.Preferred paraffinic oils or paraffin.
The preparation method of the ultra-thin high-strength MIcroporous polyolefin film of the present invention, on the basis of previous technique scheme, specifically
Be vistanex be single substance or any one containing 2 kinds or polyolefinic composition of more than two kinds.Polyolefin is preferred
Containing polyethylene and/or polyacrylic, the mean molecule quantity of vistanex is 1 × 104～1 × 107.Preferably 1 × 104～5 ×
106, it is more highly preferred to 5 × 105～5 × 106.As polyethylene, can be not limited to ultra-high molecular weight polyethylene, high density polyethylene (HDPE),
Medium density polyethylene and low density polyethylene (LDPE).These polyethylene can be Alathons or contain other alhpa olefins on a small quantity
Copolymer.
The preparation method of the ultra-thin high-strength MIcroporous polyolefin film of the present invention, on the basis of previous technique scheme, specifically
Be polyolefin powder particle size range be 0.01 μm -10 μm.Preferably 0.1 μm -2 μm.
With reference to specific embodiment, such scheme is described further.
Embodiment 1
(1) under nitrogen protection, first antioxidant is dissolved in diluent, then vistanex and diluent is added
Enter swelling dissolving in kneader.Wherein antioxidant and the mass ratio of vistanex are 1:8000, the matter of polyolefin and diluent
Amount ratio is 1:3, swelling temperature is 100 DEG C, and solution temperature is 250 DEG C.
Antioxidant in the present embodiment adopts distearyl pentaerythritol diphosphite, and vistanex is attached most importance to respectively
The polyvinyl resin with super-high molecular weight of son amount 2,000,000, diluent adopts paraffin oil.
(2) mixture obtaining swelling dissolving adds extruder by gear-conveying pump, blended dispersion and shear action,
Obtain homogeneous melt.Chilling roller is cooled to sheet material, makes polyethene microporous membrane product through biaxial tension, extraction drying etc..Squeeze
Out-of-machine temperature is 100～300 DEG C, and biaxial tension multiplying power is 7 × 8 times.It is prepared by the present embodiment that properties of product are shown in Table 1, Fig. 1
The ESEM micro-structure diagram of MIcroporous polyolefin film.
Embodiment 2
(1) under nitrogen protection, first antioxidant is dissolved in diluent, then vistanex and diluent is added
Enter swelling dissolving in kneader.Wherein antioxidant and the mass ratio of vistanex are 1:8000, the matter of polyolefin and diluent
Amount ratio is 1:3, swelling temperature is 100 DEG C, and solution temperature is 250 DEG C.
Antioxidant in the present embodiment adopts distearyl pentaerythritol diphosphite, and vistanex is attached most importance to respectively
The polyvinyl resin with super-high molecular weight of son amount 5,000,000, diluent adopts paraffin oil.
(2) mixture obtaining swelling dissolving adds extruder by gear-conveying pump, blended dispersion and shear action,
Obtain homogeneous melt.Chilling roller is cooled to sheet material, makes polyethene microporous membrane product through biaxial tension, extraction drying etc..Squeeze
Out-of-machine temperature is 100～300 DEG C, and biaxial tension multiplying power is 7 × 8 times.Properties of product are shown in Table 1.
Embodiment 3
Places different from embodiment 1 are：By the mass ratio of polyolefin and diluent by 1:3 are changed to 1:4, its properties of product is shown in
Table 1.
Embodiment 4
Places different from embodiment 1 are for the swelling temperature of polyolefin and diluent to be reduced to 80 degrees Celsius by 100 DEG C, dissolving
Temperature is reduced to 200 DEG C by 250 DEG C, and extruder temperature is 150～400 DEG C, and its properties of product is shown in Table 1.
Table 1
Tensile strength：Measured according to ASTM D882.Wherein MD represents longitudinal tensile strength, and TD represents transverse tensile strength.
The method of testing of puncture strength：Measure the pin the use of front end being sphere (radius of curvature is R=0.5mm), with 2mm/s
Speed penetrate peak load during microporous barrier.
Gas permeability：Using densometer, under 12.2 inches of oil column pressure, 100ml air passes through 1 square inch of product
Time needed for product.
It is more than that high-strength MIcroporous polyolefin film ultra-thin to the present invention and preparation method thereof is set forth, be used to help understand
The present invention, but embodiments of the present invention being not restricted to the described embodiments, any without departing from being made under the principle of the invention
Change, modify, substitute, combine, simplify, all should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of ultra-thin high-strength MIcroporous polyolefin film, it with vistanex as raw material, using Thermal inactive
Principle prepares polyolefin porous membrane it is characterised in that comprising the steps：
A. the swelling dissolving of polyolefin：Antioxidant is dissolved in diluent kneader, adds polyolefin tree into diluent
Cosmetics end is stirred uniformly, and under nitrogen protection, it is swelling to be warming up to 80 DEG C -150 DEG C insulations, obtains swelling polyolefin；In nitrogen
Under gas shielded, in swelling polyolefin, add diluent, dissolving at 100-400 DEG C forms mixture；Described antioxidant is 3-
(3,5- di-t-butyl -4- hydroxy benzenes) propionic acid stearyl, phosphorous acid dodecyl three ester, double octadecyl pentaerythrite are double
The double lauryl alcohol ester of phosphite ester, thio-2 acid or the double isomerous tridecanol ester of thio-2 acid, described antioxidant and polyolefin tree
The part by weight of fat is 1:50-10000；
B. slab：The mixture of previous step gained is sent into extruder by gear-conveying pump, using extruder plasticized mixtures
Form polyolefin solution, the polyolefin solution obtaining is extruded from die head under the control of measuring pump, obtains polyolefin melt；
C. polyolefin casting films one-off drawing：Melt cooling, after die head extrusion, is become to obtain by polyolefin melt by chilling roller
Diaphragm, then passes through biaxial orientation stretching machine and carries out biaxial tension, then extracts oil removing using diluent to diaphragm at room temperature and does
Dry；
D. polyolefin film succeeding stretch：By the diaphragm after extraction carry out again in hot-stretch case succeeding stretch or succeeding stretch with after
Sequence obtains MIcroporous polyolefin film after processing.
2. ultra-thin high-strength MIcroporous polyolefin film according to claim 1 preparation method it is characterised in that：Described polyolefin
In swelling dissolving step, in obtained mixture, vistanex and diluent weight are than for 1:1-10.
3. ultra-thin high-strength MIcroporous polyolefin film according to claim 1 preparation method it is characterised in that：Described extruder
For screw extruder, the screw speed of described screw extruder is 50-250rpm, and the operating temperature of extruder is 100-400 DEG C,
Output pressure is 10-50MPa；Chilling roller operating temperature is 5-50 DEG C；Casting films biaxial tension multiplying power is 1-10 × 2-20.
4. ultra-thin high-strength MIcroporous polyolefin film according to claim 1 preparation method it is characterised in that：Described diluent
For one or more of decahydronaphthalene, kerosene, paraffin oil, paraffin.
5. ultra-thin high-strength MIcroporous polyolefin film according to claim 1 preparation method it is characterised in that：Described diluent
For paraffin oil or paraffin.
6. ultra-thin high-strength MIcroporous polyolefin film according to claim 1 preparation method it is characterised in that：Described polyolefin
The mean molecule quantity of resin is 1 × 104～1 × 107.
7. ultra-thin high-strength MIcroporous polyolefin film according to claim 1 preparation method it is characterised in that：Described polyolefin
The particle size range of powder is 0.01 μm -10 μm.
8. a kind of MIcroporous polyolefin film by the arbitrary described preparation method preparation of claim 1～7 it is characterised in that：Polyene
The thickness of hydrocarbon microporous barrier is 5-30 μm, and porosity is 32-55%, and average pore size is 25-55 nanometer, the percent thermal shrinkage when 105 DEG C
It is more than 160MPa for being not more than 4.0, MD tensile strength, TD tensile strength is more than 150MP, air penetrability is more than 180sec/100ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410168426.8A CN103921449B (en) | 2014-04-23 | 2014-04-23 | Ultrathin high-strength polyolefin microporous film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410168426.8A CN103921449B (en) | 2014-04-23 | 2014-04-23 | Ultrathin high-strength polyolefin microporous film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103921449A CN103921449A (en) | 2014-07-16 |
| CN103921449B true CN103921449B (en) | 2017-02-15 |
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| CN112169605A (en) * | 2020-09-15 | 2021-01-05 | 上海恩捷新材料科技有限公司 | Polyolefin diaphragm, electrochemical device and preparation method of polyolefin diaphragm raw material |
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| CN108484964A (en) * | 2018-04-28 | 2018-09-04 | 青岛蓝科途膜材料有限公司 | High-strength polyethylene microporous barrier, preparation method and its application |
| CN109326761A (en) * | 2018-08-10 | 2019-02-12 | 泰州衡川新能源材料科技有限公司 | For manufacturing the composition of lithium battery diaphragm |
| CN109517213A (en) * | 2018-11-13 | 2019-03-26 | 中国科学技术大学 | A kind of polyethylene waterproof moisture permeable membrane and preparation method thereof |
| RU2711547C1 (en) * | 2018-12-29 | 2020-01-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Method of producing mesoporous mechanically sensitive polymer materials |
| CN109834961A (en) * | 2019-02-22 | 2019-06-04 | 中国科学技术大学 | A kind of preparation method of high porosity, bigger serface polyolefin porous membrane |
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| CN112063006B (en) * | 2020-09-09 | 2021-04-09 | 上海恩捷新材料科技有限公司 | Polyolefin microporous membrane and preparation method thereof |
| CN115674628B (en) * | 2022-12-30 | 2023-05-02 | 四川卓勤新材料科技有限公司 | Polyethylene ultra-thin film and preparation method thereof |
| CN117352953B (en) * | 2023-09-15 | 2024-11-22 | 江苏北星新材料科技有限公司 | Polyolefin film and preparation method thereof, battery separator and battery |
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