CN1034375A - Microporous polypropylene membrane and production method thereof - Google Patents
Microporous polypropylene membrane and production method thereof Download PDFInfo
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- CN1034375A CN1034375A CN 88105614 CN88105614A CN1034375A CN 1034375 A CN1034375 A CN 1034375A CN 88105614 CN88105614 CN 88105614 CN 88105614 A CN88105614 A CN 88105614A CN 1034375 A CN1034375 A CN 1034375A
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Abstract
The invention belongs to a kind of microporous polypropylene membrane and production method thereof that contains two component beta crystal-type nucleaters, this film is by the organic dibasic acid of 0.0001-5% weight, and the alkaline earth metal compound of 0.001-5% weight and polypropylene are formed.Through extruding or blow moulding is made basement membrane with Beta-crystalline polyacrylic resin, drawn becomes microporous membrane again.Not only production method is simple and easy, and microporous polypropylene membrane of the present invention is applicable to the alligatoring film that electrical condenser is used, and can print and write, and is used for the microporous membrane of ultrafiltration or gas delivery or separated from solvent.
Description
The present invention relates to a kind of microporous polypropylene membrane and production method thereof.Specifically, the present invention is a kind of microporous membrane of being made up of two component beta crystal-type nucleaters and polypropylene.System adopts Beta-crystalline polyacrylic to make by the feature that the generation crystal conversion that stretches causes forming a large amount of micropores.
Microcellular polymeric material is a class speciality polymer material, shows critical role day by day on chemistry, biochemistry, medical science, oil, electronics, food and isolation technique.Poromerics can be used inversion of phases, sintering, stripping or drawing process production.The inversion of phases method is promptly utilized the phase separation principle of macromolecular solution, and phase separations such as control SOLUTION PROPERTIES and solvent evaporation obtain the film in different apertures, still are widely adopted at present.But, influence scale operation owing to need a large amount of solvents, complex process.Sintering method is that controlled temperature and pressure make powder be bonded to porous material with powdery superpolymer even heating, though this method is simple, is difficult to form the little and uniform material in aperture.Stripping method is to sneak into the basement membrane of soluble substance, with solvent with the soluble substance stripping.This method products obtained therefrom aperture lack of homogeneity also need utilize solvent.United States Patent (USP) (u.S, 4386129) was once reported with quinacridine dyestuff or permanent red E3B, formed the β spherocrystal in polypropylene, again with organic solvents such as toluene optionally stripping β spherocrystal obtain microporous membrane.But the gained film is thicker, owing to using solvent, dissolution time is long and needs strict control stripping temperature to be difficult to scale operation.As everyone knows, utilize stretching or striking energy to make polypropylene generation albinism produce micropore.Once report (Polymer 29,233(1988)) when alpha-crystal form polypropylene when stretching greater than 10 millimeters/component velocity, the polypropylene albefaction produces micropore, density reduces, but density reduces not quite, porosity is very low, micropore concentrates on the surface.United States Patent (USP) (U.S.4138459) adopts the drawing process of hard elastics film to produce microporous polypropylene membrane, common alpha-crystal form polypropylene is extruded than low melting glass, and cool off fast, draw at a high speed to obtain high fusion stress, annealing forms elastica again.Longitudinal stretching makes the laminate structure distortion at a lower temperature then, becomes the seam shape space that is interweaved, and finalizes the design under comparatively high temps to increase thermostability at last.This method is easy to suitability for industrialized production, but owing to low temperature is extruded high-speed stretch and is difficult to carry out on general industry equipment, and need annealing, cold drawn, hot-drawn, heat setting type or heat lax etc., step is miscellaneous, the product poor heat stability that obtains, this method low melting glass and high shear rate be the thicker diaphragm of limit production also.Preceding method is the film-forming process complexity not only, and the porosity of gained microporous polypropylene membrane is lower, and the aperture is big, the film thickness scope is also narrower, has placed restrictions on its application.So people are still in the microporous polypropylene membrane of exploring excellent property and easy production method.
The Beta-crystalline polyacrylic, production method and the application (Chinese patent that contain two component beta crystal-type nucleaters of invention such as Shi Guanyi, Zhang Jingyun, application number 85100465, DE3610644A1, J61-71413), for the microporous polypropylene membrane of production excellent property becomes possibility.This high-load Beta-crystalline polyacrylic has higher impact resistance and toughness, and drawn causes transforming to alpha-crystal form, and the crystal formation volume-diminished easily becomes micropore.
One of purpose of the present invention provides a kind of microporous polypropylene membrane with high porosity and low apparent density.
Another object of the present invention provides a kind of simple stretch preparation method who prepares above-mentioned microporous polypropylene membrane.
The present invention is a kind of microporous polypropylene membrane that contains two component beta crystal-type nucleaters, specifically, is a kind of microporous polypropylene membrane of being made up of beta crystal-type nucleater A and B and three kinds of compositions of polypropylene.Beta crystal-type nucleater A, beta crystal-type nucleater B and polypropylene weight ratio are respectively 0.0001-5%, 0.001-5% and 90-99.9989% successively.Described beta crystal-type nucleater A is organic dibasic acid or its salt, and wherein organic dibasic acid can be the phthalic acid that ortho position, contraposition or a position replace, and also can be that molecular formula is C
nH
2n(COOH)
2Aliphatic dibasic acid, n=C
1-C
10Component B is the alkaline earth metal compound of periodictable second family, as alkaline earth metal oxide, carbonate, stearate or oxyhydroxide etc.
Microporous polypropylene membrane of the present invention has high porosity and low apparent density, is generally the 70-95% of stretching front diaphragm density, and its aperture major part is 2000
Below.Also can be controlled at 1000
Below.
The present invention also provides a kind of production method of producing above-mentioned microporous polypropylene membrane.Promptly from the Beta-crystalline polyacrylic resin of the beta crystal-type nucleater B component of the beta crystal-type nucleater component A that contains 0.0001-5% and 0.001-5% or add above-mentioned three mixture hot-extrudable or be blow molded into the Beta-crystalline polyacrylic film, again this basement membrane is become microporous polypropylene membrane through unidirectional or two-way stretch, described beta crystal-type nucleater A is organic dibasic acid or its salt, wherein organic dibasic acid can be the phthalic acid that ortho position, contraposition or a position replace, and also can be that molecular formula is C
nH
2n(COOH)
2Aliphatic dibasic acid, n=C
1-C
10Component B is the alkaline earth metal compound of periodictable second family, as alkaline earth metal oxide, carbonate, stearate or oxyhydroxide etc.
The Beta-crystalline polyacrylic resin or above-mentioned three mixture that contain aforementioned pair of component beta crystal-type nucleater can adopt any film forming processes of crystalline polypropylene that is suitable for to become diaphragm.In all technologies, the Beta-crystalline polyacrylic film is extruded or is blow molded in the slit is two kinds of comparatively suitable films.
The used Beta-crystalline polyacrylic resin of this patent is the Beta-crystalline polyacrylic resin that contains the beta crystal-type nucleater of aforementioned pair of component, all can reach the degree of crystallinity more than 40%, usually should be in the degree of crystallinity more than 50%.Crystallinity data can be measured by X light diffracting analysis, can represent the content of beta crystal with the K value.Remove the polypropylene homo beyond the region of objective existence, if when containing propylene copolymer up to other alpha-olefin of 20% gram molecular weight, present method also can be suitable for, present method also be applicable to can film forming any polymerization degree by fusion Beta-crystalline polyacrylic resin.But more suitable Beta-crystalline polyacrylic resin melting index should be between 0.5-20.Melting index adopts the method for ASTMD 1238-70, measures under 230 ℃ and 2.16 kilograms of loads.
Micropore forms and at first is decided by beta-crystalline form content in the polypropylene.When other condition is identical, the big and high more microporous membrane of porosity in the high more aperture that is easy to get more of beta-crystalline form content (being the K value).Certainly this influence to micropore character is a progressive formation.The K value hour still can produce appreciable micropore.It is high that but the general K value that stretches preceding Beta-crystalline polyacrylic film should be tried one's best, and more than 0.5, is preferably in more than 0.85 usually.
Beta-crystalline polyacrylic resin or above-mentioned three mixture are in extruding or be blow molded into β polypropylene film production method, and the principal element that influences the K value is later speed of cooling of melt film forming or temperature.Maximum in the room temperature-140 ℃ beta-crystalline form content that cooling forms.When cooling temperature was lower than room temperature or be higher than 140 ℃, beta-crystalline form content began to reduce until not having.When other condition one timing, fast speed of cooling is equivalent to low Tc, and speed of cooling is more little, and beta-crystalline form content is high more, cools off less than 160 ℃/minute speed usually all can obtain higher beta-crystalline form content, and is generally more suitable with 5-40 ℃ of/minute cooling.Cooling time is relevant with melt temperature, cooling temperature and filming condition.Generally between one second to 30 minutes.When cooling temperature below 100 ℃ the time, cooling time in several seconds are just enough.But cooling temperature is during near 130 ℃, and need one minute to 30 minutes cooling time.Certainly, prolonging cooling time will be more favourable to the formation of beta crystal, but be unaccommodated to scale operation.Table 1 is when cooling off with cooling roller, and rate of cooling is to the situation that influences of polypropylene beta phase Tc.
Table 1. rate of cooling is to the influence of polypropylene beta phase Tc
In being blow molded into membrane process, diaphragm can be used liquid bath, cooling roller or airflow cooling by the airflow cooling, in the film extrusion technology of slit.
In the method for the formation Beta-crystalline polyacrylic film of this patent, the high polymer molten temperature is generally 170-270 ℃, and better temperature is 200-240 ℃.Can change following parameter controlled chilling speed, require the diaphragm of K value in the hope of reaching, i.e. melt temperature, rate of extrusion, pulling speed, in the membrana oralis size of film extrusion, cooling air speed and temperature during the blowing film forming, chill-roll temperature during cast film.When other condition is constant, increase melt temperature, extruded velocity, membrana oralis size, cooling air temperature or chill-roll temperature, will reduce speed of cooling, and increase pulling speed and cooling air flow velocity degree will cause the increase of speed of cooling.
The inventive method required equipment is general device, as common forcing machine, film balance or inflation film manufacturing machine.As common forcing machine, as long as the slit head is housed, as T type mouth mould.When being used for form flat film, usually pour Beta-crystalline polyacrylic resin or two component beta crystal-type nucleater and polyacrylic three mixture into the forcing machine hopper, through screw rod, resin is in molten state in the mouth mould, through slit extruding film forming, cooled off, draw by transfer roller or other medium.Traction and extruded velocity can be any, but must cooperate with the speed of cooling that requires, and a mouth mould open slots width is decided with equipment, 0.20-5mm normally, pulling speed normally 0.1-150 rice/minute, with 1-20 rice/minute be advisable.Draw ratio (pulling speed/extruded velocity) is 1: 1-200: 1, and 4-20 preferably: 1.Simultaneously, extruding melt film should make it cool off than under the jogging speed with various medium coolings.Medium temperatures such as cooling roller, air or water are at 40-140 ℃, with 80-130 ℃ better, preferably 100-125 ℃.Be not less than 1 second cooling time, be advisable by 30 minutes with 1 minute.Also can adopt as other heating installation coolings such as infrared radiations.
Another feasible film is that blowing is extruded.The hopper of this equipment is extruded identical with above-mentioned slit with the forcing machine part in essence.The melt per os mould of extruding from forcing machine enters an annular slit die formation periosteum, by inlet air is blown in the periosteum the film inflation, cool down and hardening through a segment distance caudacoria, cut coiling open, mouthful mould size and blow-up ratio are different with film.The wide normally 0.20-5mm of annular mouth die slot is generally 0.4-1.2mm.Blow-up ratio (inflation caudacoria diameter/annular die diameter) is 0.5-6.0, is advisable with 1.0-2.5.Leading speed, draw ratio and melt film cooling conditions and slit extrudes same or similar.Importantly controlling above-mentioned condition makes speed of cooling in claimed range.
Can stretch and to obtain microporous polypropylene membrane containing the flat film of Beta-crystalline polyacrylic with the inventive method.Except that the micropore quality of K value impact polypropylene microporous membrane, the stretching condition that comprises draw ratio, draft temperature and speed also is an important factor.The aperture of the finished product, porosity will depend on draw ratio consumingly.Draw ratio increases makes micropore be spread at draw direction.But when stretching ratio is bigger, will further enlarge shrinking and influence micropore perpendicular to draw direction (laterally reach thickness aspect).So, have only moderate stretch ratio just can obtain satisfied aperture and porosity.Suitable draw ratio, or elongation is 10%-1000% or higher,
The general 50-400% that adopts is advisable.When uniaxial extension or twin shaft step drawing, be best with 100-300%.When twin shaft stretches simultaneously with 50-150% for well, the diaxon draw ratio preferably equates.
Usually there is certain mutual relationship between rate of extension and the temperature.When other condition was identical, fast rate of extension was corresponding to low draft temperature.In general, lesser temps and higher rate of extension easily form micropore.
The inventive method can be lower than room temperature or be higher than room temperature, stretches between 140 ℃.But room temperature tensile to obtain stretching uniform product comparatively the difficulty.And under excessive temperature, stretch, be difficult to obtain the product of micropore character preferably again.When stretching more than 120 ℃, micropore number and size will sharply reduce.When stretching more than 140 ℃, almost do not have hole and produce.General draft temperature, better when single shaft and twin shaft step drawing with 40-120 ℃.The best is 80 ℃ of 40-, and during the twin shaft synchro-draw, temperature with 80-130 ℃ better.
Influence does not have temperature so obvious to rate of extension to micropore, can both obtain the quite high product of air penetrability in very wide velocity range.Table 2 is the air penetrability data of Beta-crystalline polyacrylic extruded film microporous polypropylene membrane of friction-motion speed uniaxial extension to 200% in the time of 60 ℃ of K=0.90.Single shaft or biaxial stretch-formed speed can adopt the 0.2-1000 millimeter/minute or higher, but single shaft or twin shaft step drawing with 10-500 millimeter/minute be advisable, twin shaft stretches simultaneously with 10-100 millimeter/minute better.
Table 2. rate of extension is to N
2The influence of transmitance (60 ℃, spacing jig 5Cm)
Biaxial stretch-formed aperture porosity than uniaxial extension is generally higher.Biaxial stretch-formed can be in two vertical direction whiles or step drawing, but also alternate manner stretches, and as the circle radial drawing, level of stretch, temperature and speed are same or similar to micropore property effect rule and uniaxial extension.But studies show that biaxial stretch-formed, particularly twin shaft stretches simultaneously, difficult success under lesser temps or very high rate of extension, often sample promptly broke in the past not reaching the expection level of stretch.So twin shaft is the suitable height of draft temperature of stretch ratio uniaxial extension simultaneously, and draw speed should hang down.When adopting the twin shaft step drawing, be actually the secondary uniaxial extension, its condition is identical with uniaxial extension.
Form the Beta-crystalline polyacrylic basement membrane and be drawn into two technologies of microporous polypropylene membrane and can carry out continuously.Introduce suitable stretching device as extruded film through take off roll.This device is to allow film enter between two take off roll.Wherein the roller of back has bigger linear velocity than the roller of front.The control speed ratio can obtain different draw ratio.
The microporous polypropylene membrane that obtains after the stretching also can be finalized the design to increase its stability, promptly makes the microporous polypropylene membrane after the stretching enter a heating unit through a transfer roller again, and this take off roll speed can be lower than, identical or be higher than aforementioned second roller.Tighten through the film of this heating unit like this and do not shrink or be contracted to desired degree, the speed of controlling diaphragm turnover heating unit is promptly controlled shaping time.Above-mentioned heating unit can adopt any way, as hot-plate or case, liquid or gaseous media.But microporous polypropylene membrane of the present invention also can be handled without setting process.
As mentioned above, the stretching of Beta-crystalline polyacrylic basement membrane will be contained and microporous polypropylene membrane can be got.Stretching can be from by Beta-crystalline polyacrylic resin or contain above-mentioned pair of component beta crystal-type nucleater and polyacrylic mixture melt extrudes and carrying out continuously after forming corresponding basement membrane, also can adopt twin shaft simultaneously or the step drawing method.The simplyst carry out uniaxial extension continuously after being into basement membrane.
The microporous polypropylene membrane that contains two component beta crystal-type nucleaters with present method makes is reticulated structure usually, and reticulated structure is different with the variation of stretching conditions such as draft temperature, stretch ratio and K value.This film mean pore size is less than 1000
, about porosity 0.10-0.30, pore volume 0.15-0.50 centimetre
3/ gram, density 0.60-0.85 gram per centimeter
3, reach 10000 kilograms per centimeter along the Young's modulus of draw direction film
2About, extension at break 50-400%, tensile strength 800-2500 kilograms per centimeter
2, degree of crystallinity 0.40-0.80.Thickness is 5-250 μ.
Microporous polypropylene membrane of the present invention can be used as the insulating film of electrical condenser, when the certain micropore of control, organic solvent and pigment can penetrate film inside and don't see through, again because scattering of light effect film can be beautiful oyster white, the color printing pattern is especially bright-coloured, and does not have the problem of peeling off that exists in other plastic printing technology.Film of the present invention has high gas permeation rate, and gas with various is had certain selectivity.This film is the porous organic solvent under certain conditions, and has selectivity, and is but not moistening to water.So, can also can be used between different inter gas, the organic solvent as raincoat, tent, sleeping bag, medical bandaging material etc., the separatory membrane between organic solvent and the water.
Following embodiment will more help to understand the present invention.
Embodiment
Example 1.
To contain the Beta-crystalline polyacrylic master batch of two component beta crystal-type nucleaters, in forcing machine, be heated to 200 ℃.At the wide 1mm of mouth die slot, 5 meters/minute of pulling speeds, draw ratio are to extrude form flat film at 10: 1 o'clock, crystallization under 5 minutes conditions of air cooling.This film has K value 0.9.Again through 60 ℃, rate of extension 100mm/ branch, elongation is the oyster white film that 100% o'clock uniaxial extension obtains alligatoring.This film can be write, print.Also can be used as the insulating film that power capacitor is used.Have characteristics such as oil suction, the easy infiltration of oils.Its volume resistance is 1.5 * 10
17Ω Cmtg δ is 3.5 * 10
-4(1KHZ) and 2.5 * 10
-5(50HZ), identical with general polypropylene film.The density of this film is 0.85-0.86, is lower than general polypropylene screen (0.91).
Example 2.
The Beta-crystalline polyacrylic pellet that will contain two each 1% weight of component beta crystal-type nucleater is extruded in the forcing machine that T shape mouth mould head is housed; the wide 0.26mm of mouth die slot; stitch long 38Cm; melt temperature is 250 ℃, 0.25 meter/minute of extruded velocity, and draw ratio is 2: 1 o'clock uniaxial extensions; chill-roll temperature is 125 ℃; melt film stopped on the roller more than 30 seconds, and melt film obtains thickness by the take off roll coiling after cooling hardening on the cooling roller be 250 μ, the flat film of the Beta-crystalline polyacrylic of K value 0.90.
Should under different condition, stretch by flat film, record its density, pore volume, pore size distribution with mercury penetration method and see Fig. 1-5.Its porosity, density data such as following table:
Among the figure abscissa represent the aperture (
), the right side ordinate is represented the percentage ratio in different apertures, left side ordinate indication window volume.Stretching condition is as follows:
The result shows that comparatively high temps stretches and bigger elongation all will make porosity reduce and the aperture is less, and the distribution disperse.
Example 3.
With two flat films of component Beta-crystalline polyacrylic of containing of example 2 simulated condition gained, under differing temps, be stretched to different multiples.Its nitrogen transmitance as shown in Figure 6.Abscissa is an extensibility among the figure, and ordinate is l
gAir penetrability (centimetre
3/ rice
224 hours normal atmosphere).Very little or too high elongation is difficult to obtain higher nitrogen transmitance.When elongation was 50-350%, air penetrability can reach or be higher than 1 * 10
6The order of magnitude.And generally polypropylene screen is when respective thickness, and the nitrogen transmitance only is 10
1-10
2The order of magnitude.Usually the higher silicon rubber film maximum nitrogen transmitance of air penetrability only reaches 10
5The order of magnitude.
Fig. 7 is the relation of draft temperature to the air penetrability influence.Each sample elongation all is 200%, and abscissa is a draft temperature, and ordinate is l
gAir penetrability (centimetre
3/ rice
224 hours normal atmosphere), the result shows that the nitrogen transmitance changes little under the low draft temperature.When draft temperature during at 90 ℃, the nitrogen transmitance begins to descend, and is stretching more than 120 ℃, and the nitrogen transmitance sharply descends.The mercury pressuring data of case of comparative examples 2 can be observed the relation of nitrogen transmitance and aperture, porosity, and when promptly aperture, porosity were big, the nitrogen transmitance was also bigger.
Gas permeation rate records according to the ASTMD1434 method, because microporous polypropylene membrane nitrogen transmitance of the present invention is higher, pressure difference adopts water column to measure.Under the pressure reduction of 60Cm water column, measure.
Example 4.
Stretch under different condition by the flat film of example 2 gained Beta-crystalline polyacrylics, carry out the solvent inhalation test then.Concrete steps are the sample (W that will weigh up in advance
1) be dipped in a certain specific solvent, take out after 24 hours, carefully dry remained on surface liquid with filter paper, weigh W
2, it is (W that ordinate representation unit weight film sucks quantity of solvent
2-W
1)/(W
1) (gram/gram).
Uniaxial extension was to the solvent soakage of different elongation microporous polypropylene membranes when Fig. 8 was 60 ℃.
Fig. 9 is that uniaxial extension, extensibility are 300% o'clock, and draft temperature is to the soakage influence of n-tetradecane.
The soakage of n-tetradecane when Figure 10 is biaxial stretch-formed different elongation.△ represents 100 ℃ of stretching results, and O represents 120 ℃ of stretching results.
It is identical with air penetrability to observe its variation tendency, and uniaxial extension is similar to biaxial stretch-formed result.
Above-mentioned microporous polypropylene membrane can not suck or permeate water.Simultaneously owing to different solvents being had different suctions or seeing through.So microporous polypropylene membrane of the present invention can be used for dried up and other solvent of branch, and the separation of different solvents.
Example 5.
The similar example 2 of extrusion condition, but the used pair of component nucleator composition and content make that to obtain to extrude flat film K value only be 0.17 and 0.35.The flat film of extruding of above-mentioned flat film and example 2 gained K=0.90 is stretched under the same conditions, records the air penetrability data and see the following form:
The result shows, still has micropore to produce though stretch during K=0.17, and sample is creamy white, and air penetrability greatly reduces.In fact, in drawing process, the K value hour is difficult to stretch and obtains the uniform microporous polypropylene membrane of elongation, and the K value is easy to when high to obtain to stretch evenly and cross-sectional area shrinks less microporous polypropylene membrane.
Example 6.
The flat film of extruding of K=0.90 is stretched to 200%, 300% elongation at 60 ℃, measures its nitrogen, OTR oxygen transmission rate then, the result is as shown in the table.The result shows that oxygen has higher transmitance than nitrogen.The ratio of transmitance is about α O
2/ N
2=1.77.Illustrate that microporous polypropylene membrane of the present invention has certain separating effect to gas with various.
Example 7.
With the flat film of extruding of K=0.50 and 0.90, stretch 300% at 60 ℃, stretching 300%, obtain twin shaft step drawing microporous polypropylene membrane again perpendicular to former draw direction.This film is put into seepage basin again, and seepage basin one side is injected ethanol, toluene or other organic solvent, and adds 3 kilograms per centimeter
2Pressure can be seen that the ethanol equal solvent can be stablized to see through.And under the similarity condition, water is impermeable.
Example 8.
The extruded film condition is with example 2.Different is that chill-roll temperature is 97 ℃, in several infrared bulb irradiations of cooling roller top equipment.The ambient air temperature of cooling roller and film makes it with slower speed cooling about 80-100 ℃.The extruded film that obtains thus, the K value can reach 0.93.Get this extruded film and stretch 300% down at 80 ℃, recording its pore volume with the mercury platen press is 0.5426 centimetre
3/ gram, aperture 200-2000
Example 9.
With melting index be 9.0 the gram/10 minutes be mixed with 1%.The polypropylene of aforementioned pair of component nucleator adds and is equipped with in the single screw extrusion machine of annular die.Extrude mouthful wide 2.5mm of die slot at 210 ℃.Melt is constantly extruded the formation pipe from the mouth mould, and to use air inflation, blow-up ratio be 2.0.Periosteum through inflation is cooled off about 30 ℃ of compressed air temperature by its peripheral pressurized air.Control air speed, temperature and air position made blown tube be as cold as 80 ℃ in 1 minute.Cooled periosteum cuts and obtains film through a V-arrangement framework.By a series of nip rolls tractions, draw ratio is 50: 1 again.This film enters one 80 ℃ thermostat container, is equipped with two take off roll that linear velocity is different in the case, and the preliminary roller rotating speed is 200 meters/minute, and back roller rotating speed is 400 meters/minute.Through this two roller, film 100% the elongation that has been stretched promptly gets microporous polypropylene membrane.It is 0.2969 milliliter/gram that this film is measured pore volume by the mercury platen press, porosity 17.8%, aperture 100-700
Claims (7)
1, a kind of microporous polypropylene membrane, it is characterized in that forming by the beta crystal-type nucleater A of 0.0001-5% weight, the beta crystal-type nucleater B of 0.001-5% weight and the polypropylene of 90-99.9989%, described beta crystal-type nucleater A is organic dibasic acid or its salt, wherein organic dibasic acid can be the phthalic acid that ortho position, contraposition or a position replace, and also can be that molecular formula is C
nH
2n(COOH)
2Aliphatic dibasic acid, n=C
1-C
10, beta crystal-type nucleater B is the alkaline earth metal compound of periodictable second family, as alkaline earth metal oxide, carbonate, stearate or oxyhydroxide.
2, a kind of microporous polypropylene membrane as claimed in claim 1 is characterized in that this film mean pore size＜1000
, porosity 0.10-0.30, pore volume 0.15-0.50 centimetre
3/ gram, density 0.60-0.85 gram per centimeter
3, can reach 10000 kilograms per centimeter along the draw direction young modulus
2, extension at break 50-400%, tensile strength 800-2500 kilograms per centimeter
2, degree of crystallinity 0.40-0.80.
3, a kind of production method of microporous polypropylene membrane as claimed in claim 1, it is characterized in that to contain the beta crystal-type nucleater A of 0.0001-5% weight, the polypropylene of the beta crystal-type nucleater B of 0.001-5% weight or Beta-crystalline polyacrylic resin add hot-extrudable or are blow molded into the Beta-crystalline polyacrylic basement membrane, this basement membrane is drawn again, described beta crystal-type nucleater A is organic dibasic acid or its salt, and wherein organic dibasic acid can be the ortho position.The phthalic acid that a contraposition or a position replace also can be that molecular formula is C
nH
2n(COOH)
2Aliphatic dibasic acid, n=C
1-C
10, beta crystal-type nucleater B is the alkaline earth metal compound of periodictable second family, as alkaline earth metal oxide, carbonate, stearate or oxyhydroxide.
4, a kind of production method of microporous polypropylene membrane as claimed in claim 3 is characterized in that the described method that is extruded into the Beta-crystalline polyacrylic basement membrane, resin or mixture are through 170-270 ℃ of fusion, be preferably in 200-240 ℃ of fusion, extrude through forcing machine flat-die mouth (slit), the wide 0.20-5mm of mouth die slot, extruded film is through drawing-off, drawing speed be 0.1-150 rice/minute, with 1-20 rice/minute be advisable, ratio of drawing (drafting rate/extruded velocity) is 1: 1-200: 1, be preferably in 4-20: and 1, extruded film cools off with other medium, as cooling roller, air or water, cooling temperature is at 40-140 ℃, with 80-130 ℃ better, best 100-125 ℃, be not less than 1 second cooling time, divide with 1-30 and be advisable.
5, a kind of production method of microporous polypropylene membrane as claimed in claim 3, it is characterized in that the described method that is blow molded into the Beta-crystalline polyacrylic basement membrane, resin or mixture are through 170-270 ℃ of fusion, be preferably in 200-240 ℃ of fusion, gas is by blow moulding machine annular die blowing film forming, the annular mouth die slot is wide to be 0.20-5mm, be generally 0.4-1.2mm, blow-up ratio (inflation caudacoria diameter/annular die diameter) is 0.5-6.0, be advisable with 1.0-2.5, drawing speed, ratio of drawing and film cooling conditions are described with claim 4.
6, a kind of production method of microporous polypropylene membrane as claimed in claim 3, it is characterized in that the described membrane method that is drawn into is uniaxial extension or twin shaft step drawing, draft temperature room temperature to 140 ℃, generally better with 40-120 ℃, the optimum stretch temperature is 60-80 ℃, and elongation is 10-1000% or higher, is good with 100-300%, rate of extension be the 0.2-1000 millimeter/minute or higher, with 10-500 millimeter/be divided into good.
7, a kind of production method of microporous polypropylene membrane as claimed in claim 3, it is characterized in that the described membrane method that is drawn into is that twin shaft stretches simultaneously, draft temperature room temperature to 140 ℃, with 100-130 ℃ for well, elongation is 10-1000% or higher, with 50-150% is good, draw speed be the 0.2-1000 millimeter/minute or higher, recommend the 10-100 millimeter/minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105614 CN1009653B (en) | 1988-12-14 | 1988-12-14 | Polyacrylic microporous barrier and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105614 CN1009653B (en) | 1988-12-14 | 1988-12-14 | Polyacrylic microporous barrier and preparation process thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85100464 Division | 1988-12-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034375A true CN1034375A (en) | 1989-08-02 |
| CN1009653B CN1009653B (en) | 1990-09-19 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105614 Expired CN1009653B (en) | 1988-12-14 | 1988-12-14 | Polyacrylic microporous barrier and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1009653B (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082883C (en) * | 1996-04-26 | 2002-04-17 | 三井化学株式会社 | Porous film of high strength polypropylene and process for producing same |
| CN1304469C (en) * | 2002-08-05 | 2007-03-14 | 广东炜林纳功能材料有限公司 | Polypropylene beta crystalline form nucleator and products produced thereof |
| CN100532444C (en) * | 2006-05-12 | 2009-08-26 | 中国科学院化学研究所 | High-beta crystal content polypropylene film piece and its preparing method |
| CN101698352A (en) * | 2009-11-05 | 2010-04-28 | 江苏申龙创业集团有限公司 | Preparation method of hard elastic polypropylene film |
| CN101704299A (en) * | 2009-11-05 | 2010-05-12 | 江苏申龙创业集团有限公司 | Method for preparing polypropylene microporous membrane |
| CN101245150B (en) * | 2007-05-08 | 2010-09-22 | 中国科学院化学研究所 | Asymmetrical polypropylene porous film and process for producing same |
| CN101255236B (en) * | 2008-03-19 | 2010-11-10 | 中国科学院化学研究所 | Use of asymmetric polypropylene porous membrane |
| JP2012117078A (en) * | 2004-04-22 | 2012-06-21 | Toray Ind Inc | Microporous polypropylene film and method for producing the same |
| CN102604203A (en) * | 2012-01-18 | 2012-07-25 | 成都慧成科技有限责任公司 | Improved microporous polymer film and preparation method thereof |
| CN102660075A (en) * | 2012-04-18 | 2012-09-12 | 山东大学 | Comprehensive utilization method for aromatic carboxylic acid residues |
| CN102825805A (en) * | 2012-09-12 | 2012-12-19 | 成都芝田高分子材料有限公司 | Preparation method for microporous polypropylene membranes |
| CN101291794B (en) * | 2005-10-19 | 2013-08-28 | 东丽电池隔膜株式会社 | Process for producing multilayered microporous polyolefin film |
| CN105086144A (en) * | 2015-08-21 | 2015-11-25 | 成都慧成科技有限责任公司 | Oriented beta-polypropylene base membrane, polypropylene microporous membrane and method for manufacturing same |
| CN105328922A (en) * | 2015-11-23 | 2016-02-17 | 安徽国泰印务有限公司 | PETG membrane production technology |
| CN106229444A (en) * | 2016-07-21 | 2016-12-14 | 昆明云天化纽米科技有限公司 | A kind of pressure three-layer composite structure microporous polypropylene membrane |
| CN107718608A (en) * | 2017-07-17 | 2018-02-23 | 泉州嘉德利电子材料有限公司 | A kind of preparation method of High-temperature-rescapacitor capacitor polypropylene film |
| CN108346764A (en) * | 2017-12-12 | 2018-07-31 | 北方华锦化学工业股份有限公司 | A kind of preparation method of dry method biaxial tension lithium battery diaphragm |
| CN109036843A (en) * | 2018-08-31 | 2018-12-18 | 徐培培 | A kind of fire prevention thin film capacitor of resistance to breakdown |
| CN109415518A (en) * | 2016-06-24 | 2019-03-01 | 王子控股株式会社 | Biaxial stretch-formed polypropylene film, metallized film and capacitor |
| CN109517249A (en) * | 2018-11-27 | 2019-03-26 | 淄博润源化工有限公司 | Polyethylene nucleating agent β and its preparation method |
| CN111466810A (en) * | 2013-10-18 | 2020-07-31 | 赛尔格有限责任公司 | Porous membrane wipes and methods of making and using same |
| WO2021236573A1 (en) * | 2020-05-22 | 2021-11-25 | Celgard, Llc | Wide microporous film |
| CN114552119A (en) * | 2022-01-27 | 2022-05-27 | 佛山市盈博莱科技股份有限公司 | Lithium ion battery diaphragm and preparation method thereof |
-
1988
- 1988-12-14 CN CN 88105614 patent/CN1009653B/en not_active Expired
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082883C (en) * | 1996-04-26 | 2002-04-17 | 三井化学株式会社 | Porous film of high strength polypropylene and process for producing same |
| CN1304469C (en) * | 2002-08-05 | 2007-03-14 | 广东炜林纳功能材料有限公司 | Polypropylene beta crystalline form nucleator and products produced thereof |
| CN101880419B (en) * | 2004-04-22 | 2012-08-29 | 东丽株式会社 | Microporous polypropylene film |
| US8491991B2 (en) | 2004-04-22 | 2013-07-23 | Toray Industries, Inc. | Microporous polypropylene film and process for producing the same |
| JP2012117078A (en) * | 2004-04-22 | 2012-06-21 | Toray Ind Inc | Microporous polypropylene film and method for producing the same |
| CN101291794B (en) * | 2005-10-19 | 2013-08-28 | 东丽电池隔膜株式会社 | Process for producing multilayered microporous polyolefin film |
| US9492965B2 (en) | 2005-10-19 | 2016-11-15 | Toray Battery Separator Film Co., Ltd | Method for producing multi-layer, microporous polyolefin membrane |
| CN100532444C (en) * | 2006-05-12 | 2009-08-26 | 中国科学院化学研究所 | High-beta crystal content polypropylene film piece and its preparing method |
| CN101245150B (en) * | 2007-05-08 | 2010-09-22 | 中国科学院化学研究所 | Asymmetrical polypropylene porous film and process for producing same |
| CN101255236B (en) * | 2008-03-19 | 2010-11-10 | 中国科学院化学研究所 | Use of asymmetric polypropylene porous membrane |
| CN101704299A (en) * | 2009-11-05 | 2010-05-12 | 江苏申龙创业集团有限公司 | Method for preparing polypropylene microporous membrane |
| CN101698352A (en) * | 2009-11-05 | 2010-04-28 | 江苏申龙创业集团有限公司 | Preparation method of hard elastic polypropylene film |
| CN102604203A (en) * | 2012-01-18 | 2012-07-25 | 成都慧成科技有限责任公司 | Improved microporous polymer film and preparation method thereof |
| CN102660075B (en) * | 2012-04-18 | 2013-10-23 | 山东大学 | Comprehensive utilization method for aromatic carboxylic acid residues |
| CN102660075A (en) * | 2012-04-18 | 2012-09-12 | 山东大学 | Comprehensive utilization method for aromatic carboxylic acid residues |
| CN102825805B (en) * | 2012-09-12 | 2015-09-09 | 成都芝田高分子材料有限公司 | Polypropylene microporous membrane preparation method |
| CN102825805A (en) * | 2012-09-12 | 2012-12-19 | 成都芝田高分子材料有限公司 | Preparation method for microporous polypropylene membranes |
| CN111466810A (en) * | 2013-10-18 | 2020-07-31 | 赛尔格有限责任公司 | Porous membrane wipes and methods of making and using same |
| CN105086144B (en) * | 2015-08-21 | 2017-11-14 | 成都慧成科技有限责任公司 | It is orientated β polypropylene basement membrane, microporous polypropylene membrane and preparation method thereof |
| CN105086144A (en) * | 2015-08-21 | 2015-11-25 | 成都慧成科技有限责任公司 | Oriented beta-polypropylene base membrane, polypropylene microporous membrane and method for manufacturing same |
| CN105328922A (en) * | 2015-11-23 | 2016-02-17 | 安徽国泰印务有限公司 | PETG membrane production technology |
| CN109415518A (en) * | 2016-06-24 | 2019-03-01 | 王子控股株式会社 | Biaxial stretch-formed polypropylene film, metallized film and capacitor |
| CN109415518B (en) * | 2016-06-24 | 2021-05-18 | 王子控股株式会社 | Biaxially stretched polypropylene film, metallized film and capacitor |
| CN106229444A (en) * | 2016-07-21 | 2016-12-14 | 昆明云天化纽米科技有限公司 | A kind of pressure three-layer composite structure microporous polypropylene membrane |
| CN107718608A (en) * | 2017-07-17 | 2018-02-23 | 泉州嘉德利电子材料有限公司 | A kind of preparation method of High-temperature-rescapacitor capacitor polypropylene film |
| CN108346764A (en) * | 2017-12-12 | 2018-07-31 | 北方华锦化学工业股份有限公司 | A kind of preparation method of dry method biaxial tension lithium battery diaphragm |
| CN109036843A (en) * | 2018-08-31 | 2018-12-18 | 徐培培 | A kind of fire prevention thin film capacitor of resistance to breakdown |
| CN109517249A (en) * | 2018-11-27 | 2019-03-26 | 淄博润源化工有限公司 | Polyethylene nucleating agent β and its preparation method |
| WO2021236573A1 (en) * | 2020-05-22 | 2021-11-25 | Celgard, Llc | Wide microporous film |
| CN114552119A (en) * | 2022-01-27 | 2022-05-27 | 佛山市盈博莱科技股份有限公司 | Lithium ion battery diaphragm and preparation method thereof |
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