CN102527260A - Multi-layer polyethylene microporous membrane and preparation method thereof - Google Patents
Multi-layer polyethylene microporous membrane and preparation method thereof Download PDFInfo
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- CN102527260A CN102527260A CN2010106179708A CN201010617970A CN102527260A CN 102527260 A CN102527260 A CN 102527260A CN 2010106179708 A CN2010106179708 A CN 2010106179708A CN 201010617970 A CN201010617970 A CN 201010617970A CN 102527260 A CN102527260 A CN 102527260A
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- -1 polyethylene Polymers 0.000 title claims abstract description 58
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 48
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000004888 barrier function Effects 0.000 claims description 50
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 25
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 25
- 239000004743 Polypropylene Substances 0.000 claims description 19
- 229920001155 polypropylene Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 13
- 229920000098 polyolefin Polymers 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 206010061592 cardiac fibrillation Diseases 0.000 claims description 4
- 230000002600 fibrillogenic effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 230000002457 bidirectional effect Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims description 2
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 230000001360 synchronised effect Effects 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229920001410 Microfiber Polymers 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003658 microfiber Substances 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- 229920013716 polyethylene resin Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 229920001903 high density polyethylene Polymers 0.000 description 25
- 239000004700 high-density polyethylene Substances 0.000 description 25
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 125000005456 glyceride group Chemical group 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Laminated Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a multi-layer polyethylene microporous membrane with uniform pore diameter distribution and a preparation method thereof. The microporous membrane consists of polyethylene micro fibers, the porosity is 35-65 percent, and the pore diameter distribution is uniform. The preparation method comprises the following steps of: melting and mixing 15-55 percent by mass of polyethylene resin, 0.1-5 percent by mass of inorganic powder and 40-84.9 percent by mass of a film forming solvent; extruding through two or more layers of compound membrane heads; stretching along a machine direction by 1.2-1.8 times; rapidly cooling to realized micro-phase separation of a gel sheet, and fixing a micro-phase structure; heating and stretching the gel sheet once again to form a membrane; and removing the film forming agent from the membrane to form the multi-layer polyethylene microporous membrane. Due to the adoption of the method, the microporous membrane with high porosity, proper pore diameter size and proper pore diameter distribution can be obtained; and meanwhile, the permeability, mechanical strength, electrolyte absorption, heat resisting contractibility and hole closing performance of the microporous membrane are excellent.
Description
Technical field
The present invention relates to a kind of multilaminar polyethylene microporous barrier and manufacturing approach thereof, said multilaminar polyethylene microporous barrier has that high porosity, pore size are suitable, the characteristics of even aperture distribution, is useful in the middle of the fuel cell manufacture.
Background technology
Microporous barrier is an a kind of purposes filter medium very widely, can be used for gas separation, counter-infiltration, nanofiltration, ultrafiltration and micro-filtration etc. according to the difference in microporous barrier aperture.MIcroporous polyolefin film is because its cheap price and good mechanical performance and chemical-resistance are widely used in capacitor diaphragm, battery diaphragm and various diffusion barrier especially.
In technique known, the preparation method of existing MIcroporous polyolefin film mainly contains fusion drawn method and thermally induced phase separation.The fusion drawn method comprises molten polymer, film extrusion, and annealing increases platelet content and size, and accurate the stretching lets it form fine and close orderly micropore.The microcellular structure that the barrier film that the fusion drawn method is produced has prolate, owing to only carried out simple tension, the transverse strength of barrier film is poor.Thermally induced phase separation mainly comprises high boiling hydrocarbon liquids or low-molecular-weight material is mixed with vistanex; Heating and melting in extruder; Through extruding the casting sheet, cooling is separated, again with vertical (MDO) or twin shaft to thin slice is done orientation process; Use volatile solvent extraction liquid at last, can prepare the microporous membrane material of mutual perforation.
In order to obtain long-life battery; Battery its barrier film in long charge and discharge process is unlikely to be blocked by impurity, simultaneously in order to improve the electrolyte absorbability and the retentivity of this hydrophobic material of polyalkene diaphragm, requires barrier film to have bigger micropore size; But in order to prevent the short circuit of electrode; Especially need suppress as the generation of lithium rechargeable battery dendrite and the closed pore ability of raising barrier film, the aperture of barrier film again can not be too big, so need control the aperture of barrier film.In the present disclosed patent documentation; Have advantages of high strength with polymer and plasticizer through the be separated microporous barrier of preparation of thermic, but the aperture is little, permeability is low; When such microporous barrier is used as battery diaphragm; The power output of battery is low, and battery life is short, and this technology can be referring to Japan Patent 3347835 and 2657430.The method in another kind of control microporous barrier aperture is in prescription, to add inorganic powder such as silica, and like Japan Patent 2835365 and JP-A-2002-88188, the microporous barrier aperture that this technology obtains is bigger.
Summary of the invention
For addressing the above problem; The inventor is through further investigation; Find multilaminar polyethylene microporous barrier through adjustment polyethylene prescription and processing technology production; Have controlled aperture and uniform pore-size distribution, have excellent porosity, permeability, mechanical strength, electrolyte absorbability, heat-resisting shrinkage and closed pore performance simultaneously, the advantage that can embody prior art preferably overcomes its shortcoming simultaneously.
The object of the invention can reach through following measure:
A kind of preparation method of multilaminar polyethylene microporous barrier is used to prepare the polyethene microporous membrane of even aperture distribution, it is characterized in that comprising the steps:
(a), with PE resin, inorganic powder and film forming solvent melting mixing preparation PE solution A and B in double screw extruder;
(b), PE resin solution A and the B with fusion goes out the formation formed body through the multi-layer composite mold coextrusion head;
(c), the axial tension formed body also cools off the formation gel sheet fast;
(d), the preheating gel sheet, progressively or synchronous bidirectional stretching gel sheet, and carry out thermal finalization and handle, form the fibrillation film;
(e), the film forming solvent in the solvent extraction fibrillation film, and dry, form microporous barrier;
(f), the preheating microporous barrier, succeeding stretch and this microporous barrier of secondary thermal finalization form the multilaminar polyethylene microporous barrier.
Wherein, before the cooling forming body, axial tension formed body, stretching ratio are 1.2～1.8, and the formed body cooldown rate of cooling fast is not less than 50 ℃/min, and the gel sheet temperature of cooling is lower than 25 ℃, and the temperature difference on sheet material two surfaces is less than 3 ℃.
Used PE resin is that weight average molecular weight is 1x10
6Above ultra-high molecular weight polyethylene, perhaps weight average molecular weight is 1x10
6Above ultra-high molecular weight polyethylene and weight average molecular weight are 1x10
4～8x10
5Other polyethylene.
The PE resin can also use the mixture of being made up of above-mentioned polyethylene mixture and the outer polyolefin of polyethylene, and the outer polyolefin of described polyethylene comprises polypropylene and ternary polymerized polypropylene.
The kind of said acrylic resin comprises: Noblen, ethylene-propylene random copolymer and Ethylene-Propylene Block Copolymer.
Used inorganic powder is one or more the mixture in silica, mica, talcum, titanium oxide, aluminium oxide, the barium sulfate etc., and the average grain diameter of said inorganic powder is 0.05～0.1 μ m.
Film forming solvent is for being one or more the mixture in the atoleine, solid paraffin, soybean oil, peanut oil, olive oil, phthalic acid ester, o-phthalic acid dibutyl ester, dibutyl phthalate, glyceride.
The main points of such scheme are: this microporous barrier is a primary raw material with polyvinyl resin, inorganic powder and film forming solvent; As required; Can add various additives, for example antioxidant, antistatic additive, ultra-violet absorber or anti-caking agent etc. need only said additive and do not damage effect of the present invention.
With regard to the proportioning in the polyvinyl resin solution A, the content of polyvinyl resin in solution is preferably 15～55 (quality) % with regard to polyvinyl resin and film forming solvent, for obtaining better crystallized ability and pore-size distribution, and more preferably 20～45 (quality) %.The content of inorganic powder in solution is 0.1～2 (quality) %, in order to optimize the intensity that pierces through of microporous barrier, inorganic powder preferred 0.3～0.8 (quality) %.Film forming solvent content preferred 45～85 (quality) %, more preferably 55～80 (quality) %.In the polyvinyl resin solution A, resin preferred ultra-high molecular weight polyethylene, ternary polymerized polypropylene and high density polyethylene blends.
With regard to the proportioning in the polythylene resin solution B, the content of polythylene resin in solution is preferably 15～55 (quality) %, more preferably 20～45 (quality) % with regard to polythylene resin and film forming solvent.The content of inorganic powder in solution is 0.1～2 (quality) %, in order to optimize the intensity that pierces through of microporous barrier, inorganic powder preferred 0.3～0.8 (quality) %.Film forming solvent content preferred 45～85 (quality) %, more preferably 55～80 (quality) %.In polyethylene solution B, resin preferred ultra-high molecular weight polyethylene, ternary polymerized polypropylene and polypropylene blend.
The present invention is bilayer or three-layer polyethylene microporous barrier, its structure optimization A/B or A/B/A structure.The preferred A layer 20～30% of double-deck A/B structure microporous barrier bed thickness, B layer 70～80%.Three layers of preferred bed thickness of A/B/A structure microporous barrier: 10～20%: 60～80%: 10～20%.
The present invention compares prior art and has following advantage:
Pore size is controlled with distribution, has excellent porosity, permeability, mechanical strength, electrolyte absorbability, heat-resisting shrinkage and closed pore performance with film forming.
The specific embodiment
The present invention is the multilaminar polyethylene microporous barrier; Comprise polythylene resin layer A and polythylene resin layer B, with regard to polythylene resin at A, the content in the B layer; For improving the resistance against compression of multilaminar polyethylene microporous barrier; Select A layers of polyethylene resinoid content to be higher than the B layer, preferred A layers of polyethylene resinoid content is higher than B layer 5 (quality) %, and more preferably A layers of polyethylene resinoid content is higher than B layer 3 (quality) %.
With regard to the proportioning in the polythylene resin solution A, the content of polythylene resin in solution is preferably 15～55 (quality) % with regard to polythylene resin and film forming solvent, for obtaining better crystallized ability and pore-size distribution, and more preferably 20～45 (quality) %.The content of inorganic powder in solution is 0.1～5 (quality) %, in order to optimize the intensity that pierces through of microporous barrier, inorganic powder preferred 0.3～1.5 (quality) %.Film forming solvent content preferred 45～85 (quality) %, more preferably 55～78 (quality) %.Calculate the preferred ultra-high molecular weight polyethylene 100% of polythylene resin with polythylene resin 100%; More preferably ultra-high molecular weight polyethylene and high density polyethylene (HDPE) blend, content is respectively: 60 (quality) %, 40 (quality) %; More preferably ultra-high molecular weight polyethylene, high density polyethylene (HDPE), polypropylene and ternary polymerized polypropylene blend, content is respectively: 40 (quality) %, 45 (quality) %, 10 (quality) % and 5%.
With regard to the proportioning in the polythylene resin solution B, the content of polythylene resin in solution is preferably 15～55 (quality) %, more preferably 20～40 (quality) % with regard to polythylene resin and film forming solvent.The content of inorganic powder in solution is 0.1～5 (quality) %, in order to optimize the intensity that pierces through of microporous barrier, inorganic powder preferred 0.3～1.5 (quality) %.Film forming solvent content preferred 55～84 (quality) %, more preferably 59～79 (quality) %.Calculate with polythylene resin 100%, preferred ultra-high molecular weight polyethylene of polythylene resin and high density polyethylene (HDPE) blend, content is respectively: 30 (quality) %, 70 (quality) %; More preferably ultra-high molecular weight polyethylene, high density polyethylene (HDPE), polypropylene and ternary polymerized polypropylene blend, content is respectively: 25 (quality) %, 60 (quality) %, 10 (quality) % and 5 (quality) %.
The present invention is the multilaminar polyethylene microporous barrier, the optional A/B of its structure, and A/B/A or B/A/B, high for obtaining mechanical strength, the microporous barrier that resistance to pressure is good, preferred A/B and B/A/B structure, more preferably B/A/B structure.The microporous film layers thickness distribution is preferred: 10～20%: 60～80%: 10～20%, more preferably: 15%: 70%: 15%.
Concrete preparation method asks for an interview following embodiment:
Embodiment 1:
Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 25 (quality) %
6) and the SiO 2 powder of 0.8 (quality) % add double screw extruder (diameter: 110mm; L/D=52); (74.2 quality) % atoleine injects in the middle of double screw extruder through measuring pump, at 210 ℃, and melting mixing polythylene resin solution A under the 100r/min condition; Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 6 (quality) %
6), the high density polyethylene (HDPE) (weight average molecular weight: 8.7x10 of 14 (quality) %
4) and 0.8% SiO 2 powder add double screw extruder (diameter: 77mm; L/D=52); (79.2 quality) % atoleine injects in the middle of double screw extruder through measuring pump, at 200 ℃, and melting mixing polythylene resin solution B under the 100r/min condition; Polythylene resin solution A and B are combined into the B/A/B three-decker through T type film head; B/A/B threeply degree was than 15%: 70%: 15%, and B/A/B goes out 1.2 times of die head after-drawing, cooled off with 60 ℃/min at slab roller; B/A/B two surface temperature differences are cooled to 25 ℃ less than 2 ℃.With the gel sheet vertically horizontal distribution stretching in back earlier, stretching ratio 5x5,118 ℃ of draft temperatures; Stretch the back at 98 ℃ of thermal finalizations processing 30s, and with the atoleine in the washed with dichloromethane film, 1.2 times of dry back cross directional stretch are handled 30s 98 ℃ of thermal finalizations once more.
Embodiment 2:
Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 30 (quality) %
6) and the SiO 2 powder of 0.8 (quality) % add double screw extruder (diameter: 110mm; L/D=52); (69.2 quality) % soybean oil injects in the middle of double screw extruder through measuring pump, at 210 ℃, and melting mixing polythylene resin solution A under the 100r/min condition; Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 7 (quality) %
6), the high density polyethylene (HDPE) (weight average molecular weight: 8.7x10 of 18 (quality) %
4) and the SiO 2 powder of 0.8 (quality) % add double screw extruder (diameter: 77mm; L/D=52); (74.2 quality) % soybean oil injects in the middle of double screw extruder through measuring pump, at 200 ℃, and melting mixing polythylene resin solution B under the 100r/min condition; Polythylene resin solution A and B are combined into the B/A/B three-decker through T type film head; B/A/B threeply degree was than 15%: 70%: 15%, and B/A/B goes out 1.3 times of die head after-drawing, cooled off with 60 ℃/min at slab roller; B/A/B two surface temperature differences are cooled to 25 ℃ less than 2 ℃.With the gel sheet vertically horizontal distribution stretching in back earlier, stretching ratio 5x5,118 ℃ of draft temperatures; Stretch the back at 98 ℃ of thermal finalizations processing 30s, and with the soybean oil in the hexane wash film, 1.2 times of dry back cross directional stretch are handled 30s 98 ℃ of thermal finalizations once more.
Embodiment 3:
Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 10 (quality) %
6), the high density polyethylene (HDPE) (weight average molecular weight: 8.7x10 of 11.25 (quality) %
4), the polypropylene (weight average molecular weight: 1.0x10 of 2.5 (quality) %
6), the SiO 2 powder of ternary polymerized polypropylene and 1 (quality) % of 1.25 (quality) % adds double screw extruder (diameter: 110mm; L/D=52); 74 (quality) % atoleine injects in the middle of double screw extruder through measuring pump; At 210 ℃, melting mixing polythylene resin solution A under the 100r/min condition; Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 6 (quality) %
6), the high density polyethylene (HDPE) (weight average molecular weight: 8.7x10 of 14 (quality) %
4) and the SiO 2 powder of 1 (quality) % add double screw extruder (diameter: 77mm; L/D=52); 79 (quality) % atoleine injects in the middle of double screw extruder through measuring pump, at 200 ℃, and melting mixing polythylene resin solution B under the 100r/min condition; Polythylene resin solution A and B are combined into the B/A/B three-decker through T type film head; B/A/B threeply degree was than 15%: 70%: 15%, and B/A/B goes out 1.2 times of die head after-drawing, cooled off with 60 ℃/min at slab roller; B/A/B two surface temperature differences are cooled to 25 ℃ less than 2 ℃.With the gel sheet vertically horizontal distribution stretching in back earlier, stretching ratio 5x5,118 ℃ of draft temperatures; Stretch the back at 98 ℃ of thermal finalizations processing 30s, and with the atoleine in the normal heptane washing film, 1.2 times of dry back cross directional stretch are handled 30s 98 ℃ of thermal finalizations once more.
Embodiment 4:
Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 20 (quality) %
6), the polypropylene (weight average molecular weight: 1.0x10 of 5 (quality) %
6), 3 (quality) % ternary polymerized polypropylene and 0.5 (quality) % SiO 2 powder add double screw extruder (diameter: 110mm; L/D=52); 71.5 (quality) % glyceride injects in the middle of double screw extruder through measuring pump; At 250 ℃, melting mixing polythylene resin solution A under the 100r/min condition; Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 6 (quality) %
6), the high density polyethylene (HDPE) (weight average molecular weight: 8.7x10 of 17 (quality) %
4), 3 (quality) % ternary polymerized polypropylene and 0.5 (quality) % SiO 2 powder add double screw extruder (diameter: 77mm; L/D=52); 73.5 (quality) % glyceride injects in the middle of double screw extruder through measuring pump; At 200 ℃, melting mixing polythylene resin solution B under the 100r/min condition; Polythylene resin solution A and B are combined into the B/A/B three-decker through T type film head; B/A/B threeply degree was than 15%: 70%: 15%, and B/A/B goes out 1.3 times of die head after-drawing, cooled off with 60 ℃/min at slab roller; B/A/B two surface temperature differences are cooled to 25 ℃ less than 2 ℃.With the gel sheet vertically horizontal distribution stretching in back earlier, stretching ratio 5x5,118 ℃ of draft temperatures; Stretch the back at 98 ℃ of thermal finalizations processing 30s, and with the glyceride in the MEK washing film, 1.2 times of dry back cross directional stretch are handled 30s 98 ℃ of thermal finalizations once more.
Embodiment 5:
Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 20 (quality) %
6), the polypropylene (weight average molecular weight: 1.0x10 of 5 (quality) %
6), 3 (quality) % ternary polymerized polypropylene and 0.5 (quality) % SiO 2 powder add double screw extruder (diameter: 110mm; L/D=52); 71.5 (quality) % glyceride injects in the middle of double screw extruder through measuring pump; At 250 ℃, melting mixing polythylene resin solution A under the 100r/min condition; Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 6 (quality) %
6), the high density polyethylene (HDPE) (weight average molecular weight: 8.7x10 of 17 (quality) %
4), 3 (quality) % ternary polymerized polypropylene and 0.5 (quality) % SiO 2 powder add double screw extruder (diameter: 77mm; L/D=52); 73.5 (quality) % glyceride injects in the middle of double screw extruder through measuring pump; At 200 ℃, melting mixing polythylene resin solution B under the 100r/min condition; Polythylene resin solution A and B are combined into the B/A/B three-decker through T type film head; B/A/B threeply degree was than 15%: 70%: 15%, and B/A/B goes out 1.5 times of die head after-drawing, cooled off with 60 ℃/min at slab roller; B/A/B two surface temperature differences are cooled to 25 ℃ less than 2 ℃.With the gel sheet vertically horizontal distribution stretching in back earlier, stretching ratio 5x7,118 ℃ of draft temperatures; Stretch the back at 98 ℃ of thermal finalizations processing 30s, and with the atoleine in the normal heptane washing film, 1.2 times of dry back cross directional stretch are handled 30s 98 ℃ of thermal finalizations once more.
Comparative example 1:
Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 25 (quality) %
6) the adding double screw extruder (diameter: 110mm, L/D=52), 75 (quality) % atoleine injects in the middle of double screw extruder through measuring pump, at 210 ℃, melting mixing polythylene resin solution A under the 100r/min condition; Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 5 (quality) %
6) and the high density polyethylene (HDPE) (weight average molecular weight: 8.7x10 of 15 (quality) %
4) the adding double screw extruder (diameter: 77mm, L/D=52), 80 (quality) % atoleine injects in the middle of double screw extruder through measuring pump, at 200 ℃, melting mixing polythylene resin solution B under the 100r/min condition; Polythylene resin solution A and B are combined into the B/A/B three-decker through T type film head; B/A/B threeply degree was than 20%: 60%: 20%, and B/A/B goes out 2.5 times of die head after-drawing, cooled off with 60 ℃/min at slab roller; B/A/B two surface temperature differences are cooled to 25 ℃ less than 2 ℃.With the gel sheet vertically horizontal distribution stretching in back earlier, stretching ratio 5x5,118 ℃ of draft temperatures; Stretch the back at 98 ℃ of thermal finalizations processing 30s, and with the atoleine in the washed with dichloromethane film, 1.2 times of dry back cross directional stretch are handled 30s 98 ℃ of thermal finalizations once more.
Comparative example 2:
Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 25 (quality) %
6) the adding double screw extruder (diameter: 110mm, L/D=52), 75 (quality) % atoleine injects in the middle of double screw extruder through measuring pump, at 210 ℃, melting mixing polythylene resin solution A under the 100r/min condition; Ultra-high molecular weight polyethylene (weight average molecular weight: 6.5x10 with 5 (quality) %
6) and the high density polyethylene (HDPE) (weight average molecular weight: 8.7x10 of 15 (quality) %
4) the adding double screw extruder (diameter: 77mm, L/D=52), 80 (quality) % atoleine injects in the middle of double screw extruder through measuring pump, at 200 ℃, melting mixing polythylene resin solution B under the 100r/min condition; Polythylene resin solution A and B are combined into the B/A/B three-decker through T type film head, and B/A/B threeply degree was than 20%: 60%: 20%, and B/A/B goes out 1.2 times of die head after-drawing, cools off with 10 ℃/min at slab roller.With the gel sheet vertically horizontal distribution stretching in back earlier, stretching ratio 5x5,118 ℃ of draft temperatures; Stretch the back at 98 ℃ of thermal finalizations processing 30s, and with the atoleine in the washed with dichloromethane film, dry back cross directional stretch is doubly handled 30s 98 ℃ of thermal finalizations once more.
Each embodiment result sees table 1
Average thickness: utilize contact thickness meter, the longitudinal separation with 5mm on the width of 30cm is measured.
Closed pore temperature: use the load of thermo-mechanical analysis device with 2g, the heating rate of 5 ℃/min begins to test the sample of 10mm (TD) x3mm (MD) from room temperature, with near the temperature of the flex point that observes the fusing point as closed pore temperature.
Hot strength and tension fracture elongation rate: measure according to ASTM D882.
Puncture intensity: (radius of curvature is: diameter R=0.5mm) is the pin of 1mm, the peak load when stinging polyethene microporous membrane with the speed of 2mm/s to use spherical end surface.
Air penetrability: adopt densometer, the 100cm3 air is through 1 square inch of microporous barrier required time under 12.2 inch of water.
Percent thermal shrinkage: method of testing is carried out by standard GB/T12027-2004.After 90 ℃ of maintenance microporous barrier temperature reached 2 hours, the shrinkage factor of each polyethene microporous membrane was all surveyed on the vertical and horizontal direction 3 times, gets its mean value.
Porosity: the test of polyethylene micropore membrane porosity is pressed ASTM D-2873 standard and is carried out.
Aperture and pore-size distribution: adopt mercury injection method [U.S. health tower PoreMaster (GT) 60] to measure.
Claims (11)
1. the preparation method of a multilaminar polyethylene microporous barrier is used to prepare the polyethene microporous membrane of even aperture distribution, it is characterized in that comprising the steps:
(a), with PE resin, inorganic powder and film forming solvent melting mixing preparation PE solution A and B in double screw extruder;
(b), PE resin solution A and the B with fusion goes out the formation formed body through the multi-layer composite mold coextrusion head;
(c), the axial tension formed body also cools off the formation gel sheet fast;
(d), the preheating gel sheet, progressively or synchronous bidirectional stretching gel sheet, and carry out thermal finalization and handle, form the fibrillation film;
(e), the film forming solvent in the solvent extraction fibrillation film, and dry, form microporous barrier;
(f), the preheating microporous barrier, succeeding stretch and this microporous barrier of secondary thermal finalization form the multilaminar polyethylene microporous barrier.
2. the preparation method of multilaminar polyethylene microporous barrier according to claim 1 is characterized in that, before the cooling forming body, axial tension formed body, stretching ratio are 1.2～1.8.
3. the preparation method of multilaminar polyethylene microporous barrier according to claim 1 is characterized in that, the formed body cooldown rate of cooling fast is not less than 50 ℃/min, and the gel sheet temperature of cooling is lower than 25 ℃.
4. the preparation method of multilaminar polyethylene microporous barrier according to claim 1 is characterized in that, gel sheet is in cooling procedure, and the temperature difference on sheet material two surfaces is less than 3 ℃.
5. the preparation method of multilaminar polyethylene microporous barrier according to claim 1 is characterized in that, used PE resin is that weight average molecular weight is 1x10
6Above ultra-high molecular weight polyethylene, perhaps weight average molecular weight is 1x10
6Above ultra-high molecular weight polyethylene and weight average molecular weight are 1x10
4～8x10
5Other polyethylene.
6. the preparation method of multilaminar polyethylene microporous barrier according to claim 5 is characterized in that, the PE resin uses the mixture of being made up of above-mentioned polyethylene mixture and the outer polyolefin of polyethylene.
7. the manufacturing approach of multilaminar polyethylene microporous barrier according to claim 6 is characterized in that, the polyolefin outer as described polyethylene comprises polypropylene and ternary polymerized polypropylene.
8. the preparation method of multilaminar polyethylene microporous barrier according to claim 7 is characterized in that, the kind of said acrylic resin comprises: Noblen, ethylene-propylene random copolymer and Ethylene-Propylene Block Copolymer.
9. the preparation method of multilayer polyolefine microporous film according to claim 1 is characterized in that,
Used inorganic powder is one or more the mixture in silica, mica, talcum, titanium oxide, aluminium oxide, the barium sulfate etc.
10. the preparation method of multilayer polyolefine microporous film according to claim 9 is characterized in that, the average grain diameter of said inorganic powder is 0.05～0.1 μ m.
11. a multilaminar polyethylene microporous barrier is characterized in that, by the described preparation method's preparation of one of claim 1-10.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000049074A1 (en) * | 1999-02-19 | 2000-08-24 | Tonen Chemical Corporation | Polyolefin microporous film and method for preparing the same |
| JP3347835B2 (en) * | 1993-08-13 | 2002-11-20 | 東燃化学株式会社 | Method for producing microporous polyolefin membrane |
| CN101208198A (en) * | 2005-06-24 | 2008-06-25 | 东燃化学株式会社 | Polyethylene multilayer microporous membrane, battery separator using same, and battery |
| CN101272910A (en) * | 2005-09-28 | 2008-09-24 | 东燃化学株式会社 | Multi-layer, microporous polyethylene membrane, its production method, and battery separator |
| CN101291794A (en) * | 2005-10-19 | 2008-10-22 | 东燃化学株式会社 | Process for producing multilayered microporous polyolefin film |
| JP2008255307A (en) * | 2007-04-09 | 2008-10-23 | Tonen Chem Corp | Polyolefin multilayer microporous film, method for producing the same, separator for battery and battery |
| CN101296795A (en) * | 2005-10-24 | 2008-10-29 | 东燃化学株式会社 | Polyolefin multilayer microporous film, method for producing same and battery separator |
| CN101511589A (en) * | 2006-08-31 | 2009-08-19 | 东燃化学株式会社 | Microporous membrane, battery separator and battery |
| CN101511588A (en) * | 2006-08-31 | 2009-08-19 | 东燃化学株式会社 | Multi-layer, microporous membrane, battery separator and battery |
| CN101878109A (en) * | 2007-11-30 | 2010-11-03 | 东燃化学株式会社 | Microporous films, methods for their production, and applications thereof |
-
2010
- 2010-12-31 CN CN201010617970.8A patent/CN102527260B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3347835B2 (en) * | 1993-08-13 | 2002-11-20 | 東燃化学株式会社 | Method for producing microporous polyolefin membrane |
| WO2000049074A1 (en) * | 1999-02-19 | 2000-08-24 | Tonen Chemical Corporation | Polyolefin microporous film and method for preparing the same |
| CN101208198A (en) * | 2005-06-24 | 2008-06-25 | 东燃化学株式会社 | Polyethylene multilayer microporous membrane, battery separator using same, and battery |
| CN101272910A (en) * | 2005-09-28 | 2008-09-24 | 东燃化学株式会社 | Multi-layer, microporous polyethylene membrane, its production method, and battery separator |
| CN101291794A (en) * | 2005-10-19 | 2008-10-22 | 东燃化学株式会社 | Process for producing multilayered microporous polyolefin film |
| CN101296795A (en) * | 2005-10-24 | 2008-10-29 | 东燃化学株式会社 | Polyolefin multilayer microporous film, method for producing same and battery separator |
| CN101511589A (en) * | 2006-08-31 | 2009-08-19 | 东燃化学株式会社 | Microporous membrane, battery separator and battery |
| CN101511588A (en) * | 2006-08-31 | 2009-08-19 | 东燃化学株式会社 | Multi-layer, microporous membrane, battery separator and battery |
| JP2008255307A (en) * | 2007-04-09 | 2008-10-23 | Tonen Chem Corp | Polyolefin multilayer microporous film, method for producing the same, separator for battery and battery |
| CN101878109A (en) * | 2007-11-30 | 2010-11-03 | 东燃化学株式会社 | Microporous films, methods for their production, and applications thereof |
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|---|---|---|---|---|
| CN102774009A (en) * | 2012-08-07 | 2012-11-14 | 重庆纽米新材料科技有限责任公司 | Method for preparing polyolefin micro-porous film |
| CN103072355A (en) * | 2012-12-25 | 2013-05-01 | 深圳市冠力新材料有限公司 | Novel inorganic membrane and preparation method thereof |
| CN103551095A (en) * | 2013-10-11 | 2014-02-05 | 常州大学 | Method for preparing microporous material by particle entanglement molding |
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