CN1899805A - Method for preparing polymer micro porous film - Google Patents
Method for preparing polymer micro porous film Download PDFInfo
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- CN1899805A CN1899805A CNA2006100286682A CN200610028668A CN1899805A CN 1899805 A CN1899805 A CN 1899805A CN A2006100286682 A CNA2006100286682 A CN A2006100286682A CN 200610028668 A CN200610028668 A CN 200610028668A CN 1899805 A CN1899805 A CN 1899805A
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Abstract
The present invention belongs to the field of polymer film preparing technology, and is especially extruding and stretching process for preparing crystalline microporous polymer film. High molecular weight crystalline polymer and low molecular weight crystalline polymer in certain ratio are molten and blended, the mixture is fusing extruded and quick stretched to obtain the microporous film precursor, and the microporous film precursor is annealed, stretched and settled to obtain the microporous polymer film. The technological process has relatively relaxed conditions, and the prepared film has average pore size of 0.05-0.4 micron and high air permeability and may find its wide application in water treatment, micro filtering, artificial lung, cell diaphragm, etc.
Description
Technical field
The invention belongs to the preparing technical field of polymer film, what be specifically related to a kind of crystalline polymer microporous membrane extrudes the stretching preparation method.
Background technology
Polymer microporous film is the micropore with countless intercommunications, and the aperture is the thin polymer film of 0.01～10 μ m.The preparation method mainly contains that thermic is separated, the solution precipitation, extrude method such as stretching.The drawing process of extruding wherein is applicable to crystalline polymer, for example polyethylene, polypropylene, poly-4-methylpentene, polyformaldehyde, Kynoar etc.Its principle is that polymer is melt extruded, and makes polymer crystallization under higher draw ratio, and film is stretched forms micropore then.The advantage of this method is not introduce solvent or precipitating reagent in preparation process, can directly obtain the microporous barrier of high purity, and does not relate to the recovery of solvent, and technology is simple relatively, helps environmental protection.The microporous barrier that makes in this way the earliest by Celanese company in last century the eighties begin suitability for industrialized production.Be widely used in fields such as water treatment, micro-filtration, artificial lung, battery diaphragm now.
Extrude pulling method and prepare polymer microporous film requirement polymer crystal property is preferably arranged, and molecule segment can be orientated preferably when the fusion drawing-off, could form hard elastics structure preferably like this.Usually, the elasticity of film before stretching is good more, and the porosity of the microporous barrier that stretching obtains is high more, and micropore is even more.If select the higher polymer of molecular weight for use, though strand is easy to orientation in melt draw-down, the melt viscosity height, the wafer speed of growth is slow, forms microfibrillar structure easily, and micropore is inhomogeneous during stretching, and the transverse tensile strength of microporous barrier is lower.If select the lower polymer of molecular weight for use, then the orientation of molecule segment is lax easily when melt draw-down, can not get good hard elastics structure, therefore process conditions are required harsh, extrusion temperature, extrude process conditions such as draw ratio, cooling condition, annealing temperature, annealing time, draw speed to operate " window " less.
Summary of the invention
The objective of the invention is to propose the preparation method of the polymer microporous film that the gas permeability of a kind of process conditions wider range, film is improved.
The preparation method of the polymer microporous film that the present invention proposes, be crystalline polymer that molecular weight is high with the low crystalline polymer of molecular weight melt blending by a certain percentage, the presoma that process melt extrudes and stretching obtains microporous barrier fast obtains polymer microporous film with this presoma annealing, stretching and typing again.
The used crystalline polymer of the present invention comprises high density polyethylene (HDPE), isotactic polypropylene, poly-4-methylpentene 1, Kynoar or polyformaldehyde etc.
The used low crystalline polymer of molecular weight of the present invention refers to the polymer of common film-grade, and melt index (2.16kg load) restrains/10 fens 5～30, preferentially selects/10 minutes crystalline polymer of 7～15 grams for use.
The crystalline polymer of the HMW that the present invention is used refers to melt index and restrains/10 fens 0.4～4.5, preferentially selects/10 minutes crystalline polymer of 0.8～3 gram for use.
The low crystalline polymer of the used molecular weight of the present invention is 50: 50～99: 1 with the mixed proportion (weight meter) of the high crystalline polymer of molecular weight, and preferentially selecting ratio for use is 60: 40～96: 4.Be higher than this ratio, be difficult to obtain the film that micropore is evenly distributed, be lower than this and transverse tensile strength of film declined to a great extent than regular meeting.
The melting mixing of two kinds of different molecular weight polymers that the present invention is used can be carried out on double screw extruder, after extruding pelletizing, extrudes at single screw rod and prepares film on the film forming apparatus.Also can extrude film forming apparatus with directly adding single screw rod behind the granular mixing, melting mixing is even in extruding film-forming process.
The microporous barrier of the present invention's preparation can be a hollow fiber microporous membrane, also can be flat membranaceous microporous barrier.If it is circular that single screw rod is extruded the mouth die device employing of system film, what finally obtain will be hollow fiber microporous membrane; If mouthful mould adopts long slit, then obtain flat membranaceous microporous barrier.
The present invention is when extruding film processed, and extruding draw ratio is 100～1500, and the draw ratio of preferentially selecting for use of extruding is 150～1000.The microporous barrier presoma that obtains 5～80 ℃ of heat treatments (annealing) 0.5 minute～2 hours below melting point polymer, priority condition are following 15～45 ℃ of heat treatments (annealing) of fusing point 1 minute～45 minutes.Annealing rear film drawn is handled, and total multiplying power that stretches is 50%～200%, and draft temperature is above 5 ℃ to below the fusing point 10 ℃ of a polymer glass temperature.Can one-off drawing to the stretching ratio that needs, also can be stretched to the stretching ratio that needs several times.Stretched film is 5～50 ℃ of thermal finalizations below melting point polymer, and shaping time is 0.5 minute～1 hour.Shaping time is long or setting temperature is too high, and micropore is disappeared.Otherwise shaping time is too short or setting temperature is low excessively, can cause microporous barrier to use or deposits in the process and shrink.
The micropore average pore size of the microporous barrier that is obtained by the present invention changes with the change of type of polymer and drawing and setting condition between 0.05 to 0.4 μ m.The gas permeability of microporous barrier is at 40～270cm
3/ cm
2Between the sMPa, the microporous barrier of preparation improves a lot usually.
The specific embodiment
The invention is further illustrated by the following examples.But do not limit the present invention.
Embodiment 1
The model that Yanshan Petrochemical company is produced is (230 ℃ of the film-grade polypropylene of F600,2.16kg melt index is 10 grams/10 minutes) model of producing with Yanshan Petrochemical is that 1300 the weight ratio of polypropylene (230 ℃, the 2.16kg melt index is 1.5 grams/10 minutes) by 80/20 mixed.After double screw extruder melt blending, pelletizing, join the single screw extrusion machine casting film device of 45 millimeters of diameters, draw ratio 25,210 ℃ of die temperatures, melt draw-down than 200 condition under the film of 20 microns of thickness of preparation, the film that obtains heat treatment in 140 ℃ baking oven (annealing), the tensile elasticity response rate of different time sees Table 1.Film after the annealing is stretched to 100% at 120 ℃ again at room temperature tensile 25%, then 140 ℃ of thermal finalizations 5 minutes.The gas permeability data of the microporous barrier that obtains also are listed in the table 1.The test condition of tensile elasticity response rate is as follows: prepare tensile sample by GB/T1040-92, carry out extension recovery test, percentage elongation 50% with the speed of per minute elongation 100% on electronic tensile machine.
The gas permeability data at room temperature obtain with the soap film flowmeter test under 0.001MPa pressure reduction.Reference example in the table 1 is a film of using the polypropylene F600 preparation of not blending high molecular weight polypropylene 1300 under similarity condition.From tabulated data as can be seen under similarity condition, the elastic recovery rate height of the microporous barrier presoma that obtains by the method for present embodiment, the good permeability of the microporous barrier that obtains behind the drawing and setting.If the polypropylene 1300 (reference example) of not blending HMW in polypropylene F600, the gas permeability of the microporous barrier that then obtains is poor.Obtain higher elastic recovery rate, just need longer annealing time, thereby influence the production capacity of annealing device.
The elasticity of table 1 microporous barrier and gas permeability
| Annealing time (min) | Reference example 1 | Embodiment 1 | ||
| Elastic recovery rate (%) | Gas permeability (ml/cm 2·s·MPa) | Elastic recovery rate (%) | Gas permeability (ml/cm 2·s·MPa) | |
| 0 | 44 | - | 63 | 22 |
| 5 | 66 | 12 | 86 | 47 |
| 10 | 81 | 44 | 89 | 78 |
Embodiment 2
High density polyethylene (HDPE) 2200J (melt flow rate (MFR) 5.8 grams/10 minutes, the density 0.968g/cm of sub-petrochemical industry will be raised
3) (melt flow rate (MFR) 0.8 restrains/10 fens, density 0.952g/cm with the high density polyethylene (HDPE) 5000S that raises sub-petrochemical industry
3) mix by 60/40 weight ratio.After double screw extruder melt blending, pelletizing, join the single screw extrusion machine casting film device of 45 millimeters of diameters, draw ratio 25,170 ℃ of die temperatures, melt draw-down than 300 condition under the film of 20 microns of thickness of preparation.The film that obtains heat treatment 20 minutes in 110 ℃ baking oven, again at room temperature tensile to 150%, 120 ℃ of thermal finalizations 10 minutes, the gas permeability of the microporous barrier that obtains was 250ml/cm
2SMPa, the elastic recovery rate of microporous barrier presoma are 42%.And the gas permeability of the microporous barrier that makes under similarity condition with the high density polyethylene (HDPE) 2200J of not blending high density polyethylene (HDPE) 5000S is 78ml/cm
2SMPa, the elastic recovery rate of microporous barrier presoma only 24%.
Embodiment 3
The model that above-mentioned Yanshan Petrochemical company is produced is that film-grade acrylic resin and the model of Yanshan Petrochemical production of F600 is that 1300 acrylic resin mixes by 60/40 weight ratio.Prepare microporous barrier (annealing time is 10 minutes) by embodiment 1 same method and same fabrication process condition, the gas permeability of the microporous barrier that obtains is 65ml/cm
2SMPa, the elastic recovery rate of microporous barrier presoma are 91%, and the longitudinal tensile strength of microporous barrier is 1450MPa, and transverse tensile strength is 137MPa.As a reference example, in 45/55 ratio hybrid resin, though use the same method and the gas permeability of the microporous barrier that obtains of same fabrication process condition is reached for 62ml/cm
2SMPa, the elastic recovery rate of microporous barrier presoma reaches 92%, but the transverse tensile strength of microporous barrier only has 97MPa, can not satisfy the requirement of actual use.
Claims (5)
1. the preparation method of a polymer microporous film, it is characterized in that the crystalline polymer that molecular weight is low with the high crystalline polymer of molecular weight in 50: 50-99: 1 ratio melt blending, obtain the presoma of microporous barrier through melt extruding and stretching fast, with this presoma annealing, stretching and typing, obtain polymer microporous film again; Wherein, the crystalline polymer that described molecular weight is low is the polymer of common film-grade, and melt index is between 5～30 grams/10 minutes, and the crystalline polymer of described HMW is that melt index is at 0.4～4.5 crystalline polymer that restrains between/10 minutes.
2. preparation method according to claim 1 is characterized in that described crystalline polymer is high density polyethylene (HDPE), isotactic polypropylene, poly-4-methylpentene 1, Kynoar or polyformaldehyde.
3. preparation method according to claim 1 is characterized in that the melt blending of described two kinds of different molecular weight polymers, is to carry out on double screw extruder, after extruding pelletizing, extrudes at single screw rod and prepares film on the film forming apparatus; Perhaps extrude film forming apparatus with directly adding single screw rod after two kinds of polymeric aggregate blending, melting mixing is even in extruding film-forming process.
4, preparation method according to claim 3 is characterized in that described single screw rod extrudes the mouth mould of film forming apparatus and adopt circular rings, obtains hollow fiber microporous membrane, perhaps adopts long slit, obtains flat membranaceous microporous barrier.
5. preparation method according to claim 3, it is characterized in that when screw rod is extruded the preparation film, extruding draw ratio is between 100～1500, the microporous barrier presoma that obtains 5～80 ℃ of heat treatment 0.5 minute～2 hours below melting point polymer, annealing rear film drawn is handled, total multiplying power that stretches is 50%～200%, and draft temperature is above 5 ℃ to below the fusing point 10 ℃ of a polymer glass temperature; Stretched film is 5～50 ℃ of thermal finalizations below melting point polymer, and shaping time is 0.5 minute～1 hour.
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| CN2006100286682A CN1899805B (en) | 2006-07-06 | 2006-07-06 | Method for preparing polymer micro porous film |
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| CN2006100286682A CN1899805B (en) | 2006-07-06 | 2006-07-06 | Method for preparing polymer micro porous film |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954738A (en) * | 2010-09-16 | 2011-01-26 | 湖南紫皇冠新能源技术服务有限公司 | Method for preparing polymer microporous membrane for lithium ion battery |
| CN102209751A (en) * | 2008-11-19 | 2011-10-05 | 三井化学株式会社 | Polyolefin resin composition and applications thereof |
| CN102769115A (en) * | 2012-08-02 | 2012-11-07 | 常州大学 | Lithium ion battery membrane prepared by polypropylene mixture and preparing method thereof |
| CN103131080A (en) * | 2013-02-20 | 2013-06-05 | 深圳中兴创新材料技术有限公司 | Polypropylene microporous membrane and preparation method thereof |
| CN103772902A (en) * | 2014-01-28 | 2014-05-07 | 杭州师范大学 | Polyformaldehyde nanopore film with micro-nano bicontinuous porous structure and preparation method of polyformaldehyde nanopore film |
| CN104022249A (en) * | 2014-06-26 | 2014-09-03 | 佛山市盈博莱科技有限公司 | Three-layer lithium battery diaphragm and preparation method thereof |
| CN104151752A (en) * | 2014-08-28 | 2014-11-19 | 东莞市长安东阳光铝业研发有限公司 | Preparation method and application of master batch used for polyvinylidene fluoride film |
| CN109935759A (en) * | 2018-12-29 | 2019-06-25 | 深圳中兴新材技术股份有限公司 | A kind of preparation method and battery diaphragm of low thermal shrinkage battery diaphragm |
| CN110054855A (en) * | 2019-02-18 | 2019-07-26 | 浙江格尔泰斯环保特材科技股份有限公司 | A kind of polytetrafluoroethylene (PTFE) bubble point film and preparation method thereof |
| CN114211789A (en) * | 2021-11-12 | 2022-03-22 | 北方华锦化学工业股份有限公司 | Method for improving resilience rate of lithium battery diaphragm |
-
2006
- 2006-07-06 CN CN2006100286682A patent/CN1899805B/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102209751A (en) * | 2008-11-19 | 2011-10-05 | 三井化学株式会社 | Polyolefin resin composition and applications thereof |
| US8349957B2 (en) | 2008-11-19 | 2013-01-08 | Mitsui Chemicals, Inc. | Polyolefin resin composition and uses thereof |
| CN102209751B (en) * | 2008-11-19 | 2013-08-28 | 三井化学株式会社 | Polyolefin resin composition and applications thereof |
| CN101954738A (en) * | 2010-09-16 | 2011-01-26 | 湖南紫皇冠新能源技术服务有限公司 | Method for preparing polymer microporous membrane for lithium ion battery |
| CN102769115A (en) * | 2012-08-02 | 2012-11-07 | 常州大学 | Lithium ion battery membrane prepared by polypropylene mixture and preparing method thereof |
| CN102769115B (en) * | 2012-08-02 | 2015-05-13 | 常州大学 | Lithium ion battery membrane prepared by polypropylene mixture and preparing method thereof |
| CN103131080A (en) * | 2013-02-20 | 2013-06-05 | 深圳中兴创新材料技术有限公司 | Polypropylene microporous membrane and preparation method thereof |
| CN103131080B (en) * | 2013-02-20 | 2015-05-27 | 深圳中兴创新材料技术有限公司 | Polypropylene microporous membrane and preparation method thereof |
| CN103772902B (en) * | 2014-01-28 | 2015-09-09 | 杭州师范大学 | One has micro-nano co-continuous vesicular structure polyoxymethylene nano-porous thin film and preparation method thereof |
| CN103772902A (en) * | 2014-01-28 | 2014-05-07 | 杭州师范大学 | Polyformaldehyde nanopore film with micro-nano bicontinuous porous structure and preparation method of polyformaldehyde nanopore film |
| CN104022249A (en) * | 2014-06-26 | 2014-09-03 | 佛山市盈博莱科技有限公司 | Three-layer lithium battery diaphragm and preparation method thereof |
| CN104151752A (en) * | 2014-08-28 | 2014-11-19 | 东莞市长安东阳光铝业研发有限公司 | Preparation method and application of master batch used for polyvinylidene fluoride film |
| CN104151752B (en) * | 2014-08-28 | 2016-06-01 | 东莞市长安东阳光铝业研发有限公司 | The preparation method of a kind of polyvinylidene difluoride film Masterbatch and application |
| CN109935759A (en) * | 2018-12-29 | 2019-06-25 | 深圳中兴新材技术股份有限公司 | A kind of preparation method and battery diaphragm of low thermal shrinkage battery diaphragm |
| CN109935759B (en) * | 2018-12-29 | 2022-03-15 | 深圳中兴新材技术股份有限公司 | Preparation method of low-thermal-shrinkage battery diaphragm and battery diaphragm |
| CN110054855A (en) * | 2019-02-18 | 2019-07-26 | 浙江格尔泰斯环保特材科技股份有限公司 | A kind of polytetrafluoroethylene (PTFE) bubble point film and preparation method thereof |
| CN110054855B (en) * | 2019-02-18 | 2021-10-15 | 浙江格尔泰斯环保特材科技股份有限公司 | Polytetrafluoroethylene bubble point membrane and preparation method thereof |
| CN114211789A (en) * | 2021-11-12 | 2022-03-22 | 北方华锦化学工业股份有限公司 | Method for improving resilience rate of lithium battery diaphragm |
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