CN1243784C - Polyolefine multiple micoporous film and preparing process thereof - Google Patents
Polyolefine multiple micoporous film and preparing process thereof Download PDFInfo
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Abstract
The present invention discloses a polyolefine micoporous film and a preparation method thereof. The polyolefine micoporous film is a micoporous film, the pore diameter of a micopore is 20 to 500 nm, the total porosity is 30 to 60%, the film thickness is 0.5 to 25 mu m, the film strength is larger than 1700 kg/cm<2> when the film is stretched along a plane surface, and the polyolefine micoporous film has the shrinkage performance that the micropore is completely closed when the temperature is larger than 100 DEG C. The preparation method of the polyolefine micoporous film comprises: (1) polyolefin original film preparation; (2) original film annealing; (3) single time stretching and pore formation; (4) film forming. The present invention stretches an original film in a stage by changing and optimizing parameters, such as original film stretching speed change, stretching rate change, etc., and the film with thin performance and high stretching intensity is obtained. The micoporous film can be used as partition films of chemical power sources, and the working safety of the chemical power sources is guaranteed; meanwhile, the micoporous film can also be used as partition films of capacitors, basal films of various coatings, micro-filtration films, separation films, medical clothing and bandages, etc.
Description
Technical field
The present invention relates to a kind of microporous membrane of making by polyolefine, be specifically related to polyolefin microporous membrane and preparation method thereof, say exactly to relate to a kind of many microporous polyolefin films by the stretching method preparation.
Background technology
Many micropore polyolefins film is a kind of functional high molecule material, can be as basement membrane, microfiltration membrane, separatory membrane, medical clothes and the bandage etc. of the barrier film of chemical power source, the barrier film of electrical condenser, various coatings.Many micropore polyolefins film can pass through stripping method, thermally induced phase separation and stretching method production.Stripping method is a kind ofly to be filled in the method that inorganic particle is produced microporous film in the polyolefin film by stripping, and the microporous film main drawback that this method is produced is: the aperture is bigger, and skewness is mainly used in products such as diaper, sanitary towel at present.Thermally induced phase separation is to be beneficial to superpolymer and some high boiling micromolecular compound forms homogeneous phase solution under higher temperature conditions, reducing temperature is separated solid liquid of homogeneous phase solution generation and liquid-liquid, by methods such as extraction, decompressions micromolecular compound is removed, carry out the microporous film that two-way stretch obtains then under certain condition, this method is widely adopted at present.Its shortcoming is: complex process, facility investment is bigger, needs a large amount of solvents.As everyone knows, utilize stretching or ballistic method can make polypropylene generation albinism produce micropore, at present, existing numerous document or patent report polypropylene microporous film and preparation method thereof, its general step comprises: the preparation and the curing (crystallization) of the former film of (1) polypropylene (proportion is 0.91 gram/cubic centimetre), the thermal treatment of (2) former film, (3) two stage longitudinal stretching (cold stretching and thermal stretch), draw speed is less than 400%/min, and (4) microporous film carries out heat setting type to be handled.According to published patent data data US3558764, US3679538, US3843761, US4138459, the trade mark of CN1034375A, CN1134043A and the Hoechst CelaneseCorporation of u s company be Celgard product description as can be known, these polypropylene microporous membrane films have following defective as battery diaphragm:
1. film strength is not high, is generally less than 1500kg/cm
2(along mechanical stretching direction TD direction) influences work-ing life of film.
The TD direction: the direction along mechanical stretching is promptly vertical.
The MD direction: direction vertical and mechanical stretching is promptly horizontal.
2. up to the present thickness also exists the problem that former film advances to split less than the polypropylene microporous film of 20 μ m, thereby thereby the internal resistance that just can not reduce chemical power source limited the Application Areas of polypropylene microporous film.
3. the polypropylene microporous film porosity that can reach is lower, generally is no more than 50%, is difficult to adapt to the high-power requirement of battery.
4. the closed pore temperature of polypropylene microporous film higher (～140 ℃), the fusing point of itself and metallic lithium is comparatively approaching, can not guarantee can play when the lithium battery interior temperature raises rapidly isolated positive and negative electrode effect when it uses separately.Therefore polypropylene diaphragm can not play the outage effect when chemical power source is overheated, guarantees the safety of battery.
The defective of above-mentioned polypropylene microporous film is relevant with polyacrylic characteristic, and this makes and overcomes very difficult that these defectives become, some defective or even can not overcome.Therefore Hoechst CelaneseCorporation begins to attempt preparation polyethylene microporous film (US4620956).This production method is for (proportion is 0.96g/cm with the linear polyethylene melts by the blown film method
3) make certain thickness tubular film (200 ℃ of temperature, stretch ratio 20～200); Under the condition that is lower than 10～50 ℃ of melting temperatures, anneal; Two stage longitudinal stretching: vertically cold stretching (20～70 ℃ ,≤200%, draw speed≤440%/min) and thermal stretch (120 ℃ ,≤300%, draw speed 40-110%/min); The gained microporous membrane is carried out heat setting type to be handled.This production technique more complicated, productive rate is lower, and cost is higher, and film is thicker, and is all once poor.
In sum, up to the present, obtain high strength (＞1700kg/cm
2) particularly thickness is less than 20 μ m for microporous polyolefin film, many micropore polyolefins film of following perviousness to disappear in the time of 100 ℃ is not also reported.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of polyolefin microporous membrane, and to overcome the complex manufacturing that prior art exists, productive rate is lower, and cost is higher, film thicker, all once poor, the defective that intensity is low;
Two of the technical issues that need to address of the present invention provide the preparation method of said polyolefins microporous membrane.
Technical scheme of the present invention:
Polyolefine microporous film of the present invention is a kind of microporous film that has, and the aperture of micropore is 20～500nm, and total porosity 30%～60%, film thickness are 0.5～25 μ m, and film strength is 1700～2100kg/cm during along planar stretch
2, temperature during greater than 100 ℃ microporous film shrink that to show as micropore closed fully.
Preferred polyolefine is polyethylene, polypropylene and tetrafluoroethylene, and most preferred is polyethylene.
The polyolefinic Mw (molecular mass) that is addressed is 10000～1000000, is preferably: 50000～300000; Molecular weight distribution (Mw/Mn) is 1～40, is preferably 3～10; Density is 0.90～3g/cm
3, be preferably 0.91～0.97g/cm
3Melting index is 0.1～20 gram/10 minutes, is preferably: 0.3～10.0.
The preparation method of polyolefine microporous film of the present invention comprises the steps:
(1) preparation of the former film of polyolefine:
The raw material polyolefine is melted in forcing machine, the die orifice of the cast film machine of fused polyolefine by having the T die head, cooling can be cooled off fast by cooling roller or air fast, and the company of stretching forms the former film of polyolefine fast simultaneously;
Die temperature is: 150～420 ℃, be preferably 190～210 ℃; Die gap is 0.1～1.5mm, is preferably 0.4～1.0mm; The temperature of cooling roller is: 20～30 ℃; Stretch ratio 10～45 is preferably 10～25; Former film thickness is 1～100 μ m, is preferably 20～50 μ m; Thickness deviation is controlled at ± 3% scope in.
(2) annealing of the former film of polyolefine:
The former film of polyolefine is annealed by continuous or step annealing device, and annealing temperature is following 0～50 ℃ of a polyolefine fusing point; Annealing time is 5 minutes～12 hours.
(3) stretch forming:
The many micropores of polyolefine are two-way or longitudinal stretching formation by the former film of polyolefine after the annealing is carried out under the condition of homo(io)thermism.The former film of polyolefine after the annealing is carried out two-way or longitudinal stretching, obtain to have microporous polyolefin film, draft temperature is-20～90 ℃, is preferably 10～90 ℃, and stretching ratio is 50～600%, is preferably 100～500%; Draw speed 300～1200%/min is preferably 400～1000%/min.
Term " two-way or longitudinal stretching " refers to:
The stretching of film: in the production process of film in order to make film arrive desired tensile strength, will stretch to cast film, iff stretching along operating direction, generally be referred to as longitudinal stretching, if, generally be referred to as two-way stretch carrying out successively with operating direction or stretching simultaneously with vertical along operating direction.
The stretching of film is carried out on general drawing machine.
(4) typing:
Polyolefine microporous film after stretching is carried out thermal-setting in continuous or step device.Can obtain said polyolefine microporous film of the present invention.Fixing time is 5 minutes～12 hours; Setting temperature is following 0～50 ℃ of a polyolefine fusing point.
Can in baking oven, carry out film annealing and thermal-setting.
The many micropore polyolefins film that is obtained is tested, and the result shows that the aperture of its micropore is 20～500nm, and total porosity 30%～60%, film thickness are 0.5～25 μ m, and film strength is greater than 1700kg/cm during along planar stretch
2, its optimized polyethylene microporous film temperature during greater than 100 ℃ film shrink that to show as micropore closed fully.
The polyolefine raw material of being addressed is preferably particle or polyethylene powder, and its content should be big by 98%.
The intensity of film records on universal strength testing machine.
The film air is measured according to the Gurley method.
Pore size according to determination of electron microscopy.
Film thickness is measured by the digital vertical optical meter of JDG-S1.
By above-mentioned disclosed technical scheme as seen, the present invention passes through to change and the optimization method parameter, as changes former film draw speed etc., and former film longitudinal stretching is placed on stage stretches and carry out, promptly change drawing process, caused material reinforcement, thereby obtained film thin, that elastic strength is big.
The many micropore polyolefins film that adopts method of the present invention to obtain has very excellent properties, is a kind of barrier film of chemical power source efficiently, because film thickness is reduced to below the 20 μ m, its intensity increases to 1700kg/cm
2More than, and rate of permeation does not reduce.This invention can reduce film thickness on the one hand because the tensile strength of film improves, and makes to make minicell or high-power battery becomes possibility, has prolonged barrier film work-ing life simultaneously.Optimum microporous polyethylene film can be accepted bigger contraction (5～30%) among the present invention on the other hand, and follow the complete closure of open-work, its closed temperature (100 ℃) is more much lower than polypropylene film temperature (140 ℃), has guaranteed the security of chemical power source work.
Description of drawings
Fig. 1 is the electron micrograph of polyethylene microporous polyethylene film.
Embodiment
Embodiment 1
With linear polyethylene (Mw=230,000, Mw/Mn=2-8) the chamber screw extrusion press is made former film by experiment, temperature is 190 ℃, extensibility is 16.Former film annealing, duration 5 hours, 120 ℃ of temperature.Then to wide for the former film of 50mm carries out vertical cold stretching 400%, draw speed 400%/minute, room temperature condition.The characteristic of gained film is as follows: void content 60%, and the micropore size is 80-200nm, and thickness is 13 μ m, and air is 15sec/100cc, and TD direction intensity is 2100kg/cm
2, MD direction intensity is 250kg/cm
2, 100 ℃, free shrinkage was 35% in 60 minutes.Its electron micrograph such as Fig. 1.
Embodiment 2
With linear polyethylene (Mw=230,000, Mw/Mn=2-8) the chamber screw extrusion press is made former film by experiment, temperature is 190 ℃, extensibility is 16.Former film annealing, duration 5 hours, 120 ℃ of temperature.Then be to wide for the former film of 50mm carries out vertical cold stretching 400%, draw speed 250%/minute, room temperature condition.The gained microporous membrane is done heat setting type handle duration 5 hours, 105 ℃ of temperature.The characteristic of gained film is as follows: void content 50%, and the micropore size is 50-200nm, and thickness is 15 μ m, and air is 23sec/100cc, and TD direction intensity is 1900kg/cm
2, MD direction intensity is 210kg/cm
2, 100 ℃, free shrinkage was 38% in 60 minutes.
Embodiment 3
With linear polyethylene (Mw=230,000, Mw/Mn=2-8) the chamber screw extrusion press is made former film by experiment, temperature is 200 ℃, extensibility is 23.Former film annealing, duration 5 hours, 120 ℃ of temperature.Then be to wide for the former film of 50mm carries out vertical cold stretching 200%, draw speed 800%/minute, room temperature condition.The gained microporous membrane is done heat setting type handle duration 5 hours, 105 ℃ of temperature.The characteristic of gained film is as follows: void content 40%, and the micropore size is 20-200nm, and thickness is 10 μ m, and air is 28sec/100cc, and TD direction intensity is 1700kg/cm
2, MD direction intensity is 180kg/cm
2, 100 ℃, free shrinkage was 41% in 60 minutes.
Embodiment 4
With linear polyethylene (Mw=230,000, Mw/Mn=2-8) the chamber screw extrusion press is made former film by experiment, temperature is 210 ℃, extensibility is 27.Former film annealing, duration 5 hours, 120 ℃ of temperature.Then be to wide for the former film of 50mm carries out vertical cold stretching 400%, draw speed 340%/minute, room temperature condition.The gained microporous membrane is done heat setting type handle duration 5 hours, 105 ℃ of temperature.The characteristic of gained film is as follows: void content 40%, and the micropore size is 50-500nm, and thickness is 23 μ m, and air is 26sec/100cc, and TD direction intensity is 1700kg/cm
2, MD direction intensity is 180kg/cm
2, 100 ℃, free shrinkage was 15% in 60 minutes.
Embodiment 5
With tetrafluoroethylene (Mw=40,000, Mw/Mn=1-3) the chamber screw extrusion press is made former film by experiment, temperature is 390 ℃, extensibility is 18.Former film annealing, duration 5 hours, 330 ℃ of temperature.Then be to wide for the former film of 50mm carries out vertical cold stretching 400%, draw speed 400%/minute, room temperature condition.The gained microporous membrane is done heat setting type handle duration 5 hours, 330 ℃ of temperature.The characteristic of gained film is as follows: void content 60%, and the micropore size is 50-300nm, and thickness is 13 μ m, and air is 19sec/100cc, and TD direction intensity is 3000kg/cm
2, MD direction intensity is 250kg/cm
2, 240 ℃, free shrinkage was 5% in 60 minutes.
Claims (9)
1. a polyolefin microporous membrane is characterized in that, the aperture of micropore is 20～500nm, and total porosity 30%～60%, film thickness are 0.5～25 μ m, temperature during greater than 100 ℃ microporous film shrink that to show as micropore closed fully.
2. microporous membrane according to claim 1 is characterized in that, polyolefine is polyethylene, polypropylene and tetrafluoroethylene.
3. microporous membrane according to claim 2 is characterized in that, polyolefine is a polyethylene.
4. microporous membrane according to claim 2 is characterized in that, polyolefinic molecular mass is 10000～1000000; Molecular weight distribution is 1～40; Density is 0.90～3g/cm
3Melting index is 0.1～20 gram/10 minutes.
5. microporous membrane according to claim 4 is characterized in that, polyolefinic molecular mass is 50000～300000; Molecular weight distribution is 3～10; Density is 0.91～0.97g/cm
3Melting index is 0.3～10.0 gram/10 minutes.
6. according to the preparation method of each described microporous membrane of claim 1～5, it is characterized in that comprising the steps:
(1) preparation of the former film of polyolefine:
The raw material polyolefine is melted in forcing machine, the die orifice of the cast film machine of fused polyolefine by having the T die head, cooling stretches and forms the former film of polyolefine fast;
Die temperature is: 150～420 ℃, die gap is 0.1～1.5mm, and cooling temperature is: 20～30 ℃; Stretch ratio 10～45;
(2) annealing of the former film of polyolefine:
The former film of polyolefine is annealed by continuous or step annealing device, and annealing temperature is following 0～50 ℃ of a polyolefine fusing point; Annealing time is 5 minutes～12 hours;
(3) stretch forming:
The former film of polyolefine after the annealing is carried out two-way or longitudinal stretching under same temperature condition, obtain to have microporous polyolefin film, draft temperature is-20～90 ℃, and stretching ratio is 50～600%, draw speed 300～1200%/min;
(4) typing:
Polyolefine microporous film after stretching is carried out thermal-setting in continuous or step device; Can obtain the said polyolefine microporous film of the present invention.
7. the preparation method of microporous membrane according to claim 6 is characterized in that die temperature is 190～210 ℃; Die gap is 0.4～1.0mm; Stretch ratio 10～25.
8. the preparation method of microporous membrane according to claim 6 is characterized in that the former film of polyolefine after the annealing is carried out two-way or longitudinal stretching, and draft temperature is 10～90 ℃, and stretching ratio is 100～500%; Draw speed is 400～1000%/min.
9. the preparation method of microporous membrane according to claim 6 is characterized in that fixing time is 5 minutes～12 hours; Setting temperature is following 0～50 ℃ of a polyolefine fusing point.
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