CN103978705B - A kind of microporous polypropylene membrane method for annealing - Google Patents
A kind of microporous polypropylene membrane method for annealing Download PDFInfo
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- CN103978705B CN103978705B CN201410222102.8A CN201410222102A CN103978705B CN 103978705 B CN103978705 B CN 103978705B CN 201410222102 A CN201410222102 A CN 201410222102A CN 103978705 B CN103978705 B CN 103978705B
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Abstract
The invention discloses a kind of microporous polypropylene membrane method for annealing, comprise the steps: step one: the polypropylene prefabricated membrane with certain orientation prepared by extrusion curtain coating forming method is placed on process annealing 6～24h in the baking oven at the arbitrary temperature in 50 DEG C to 80 DEG C temperature ranges；Step 2: in crystalline region differently-oriented directivity, the prefabricated membrane after process annealing is applied 1N～2N pretightning force, and be placed in the baking oven of 130～140 DEG C high annealing 40min～1h.Microporous membrane prepared by the present invention has greatly improved in porosity, hole number, hole dimension, pore size distribution and moisture-vapor transmission, microporous membrane dimensional stability each side than the microporous membrane prepared with traditional annealing methods；The parameters such as the porosity of microporous membrane of preparation, hole number, hole dimension, pore size distribution and moisture-vapor transmission are possible not only to be adjusted by high temperature anneal temperature and time, regulate also by controlling stress relief annealed temperature and time.
Description
Technical field
Present invention relates particularly to a kind of microporous polypropylene membrane method for annealing, be specifically related to the Novel disk withdrawal ignition method of a kind of polypropylene microporous film properties that can be effectively improved dry process, belong to the preparing technical field of microporous polypropylene membrane.
Background technology
Microporous membrane refers to that having aperture is 0.01 μm of thin film to 10 μm of micropores.It is widely used in Treatment of Industrial Water, blood plasma separation, battery diaphragm, chemical products purification, fresh-keeping plastic bag, artificial organ, desalinization, textile garment, building and agricultural etc..
The preparation method of microporous membrane can be divided into two kinds generally according in the preparation process of microporous membrane with or without use solvent: wet method and dry method.Compared with wet method, the preparation process of dry method because do not have solvent participation and cheap, technique is simple and free of contamination advantage, therefore favored by people.In the process of dry process microporous membrane, annealing is the indispensable step successfully preparing microporous membrane.Traditional annealing way is the prefabricated membrane with orientation texture to be placed near melting point polymer in the baking oven of temperature high annealing increase the degree of orientation of prefabricated membrane crystalline region, degree of perfection.And the height of the crystalline region degree of orientation directly determines microcellular structure and the performance of the final microporous membrane prepared.When using traditional method for annealing, crystalline region degree of orientation increase rate is about 10%～15%.Additionally, conventional dry is prepared in microporous membrane process, make prefabricated membrane that dimensional contraction easily to occur in annealing process because of prefabricated membrane not being applied stress in annealing process.
Summary of the invention
It is an object of the invention to provide a kind of Novel disk withdrawal ignition method suitable in dry process microporous membrane is processed, not only make crystalline region degree of orientation increasing degree double compared to traditional annealing way, and ensure that the change of size does not occur prefabricated membrane in annealing process.Just because of the Novel disk withdrawal ignition method of the present invention has above good characteristic, so using the microporous membrane that the microporous membrane that the present invention prepares is prepared compared with traditional annealing methods: porosity doubles, hole dimension doubles, moisture-vapor transmission improves two to three times.
The present invention is achieved in that
A kind of microporous polypropylene membrane method for annealing, comprises the steps:
Step one: the polypropylene prefabricated membrane with certain orientation prepared by extrusion curtain coating forming method is placed on process annealing 6～24h in the baking oven at the arbitrary temperature in 50 DEG C to 80 DEG C temperature ranges；
Step 2: in crystalline region differently-oriented directivity, the prefabricated membrane after process annealing is applied 1N～2N pretightning force, and be placed in the baking oven of 130～140 DEG C high annealing 40min～1h.
The invention have the advantages that
(1) microporous membrane using the annealing preparation of above-mentioned two-step method has greatly improved in porosity, hole number, hole dimension, pore size distribution and moisture-vapor transmission, microporous membrane dimensional stability each side than the microporous membrane prepared with traditional annealing methods；
(2) parameters such as the porosity of the microporous membrane prepared, hole number, hole dimension, pore size distribution and moisture-vapor transmission are possible not only to be adjusted by high temperature anneal temperature and time, regulate also by controlling stress relief annealed temperature and time.
Further, the present invention can be made up of technical scheme concrete as follows, and following technical scheme is the refinement of abovementioned steps one and two and supplements.
A kind of microporous polypropylene membrane method for annealing, comprises the steps:
(1) with single screw extrusion machine through slit shape die extrusion polypropylene melt film, melt film obtains the prefabricated membrane with crystalline region orientation texture through air knife or natural cooling and carry-over pinch rolls traction；(2) being placed in baking oven by the polypropylene prefabricated membrane with certain degree of orientation process annealing 6～24h, oven temperature arranges the arbitrary temperature ranging in 50 DEG C to 80 DEG C；(3) along crystalline region differently-oriented directivity, the prefabricated membrane after process annealing is applied the pretightning force of 1N～2N, and is placed in the baking oven of 130～140 DEG C high annealing 40min～1h；(4) by the at room temperature quickly cold stretch of the prefabricated membrane after annealing；(5) again by the at high temperature hot-stretch of the sample after cold stretch；(6) by the heat fixation under clamp position of the sample after hot-stretch.
The present invention is indispensable in the process of dry process microporous membrane, can increase substantially the porosity of microporous membrane, hole number, hole dimension, is the effective means improving pore size distribution uniformity and moisture-vapor transmission.Prefabricated membrane size and shape after annealing by the present invention all remains stable for.When using the present invention, the increase rate of the prefabricated membrane crystalline region degree of orientation is 1.5～3 times when using traditional annealing methods.
Accompanying drawing explanation
Fig. 1 is the microcellular structure schematic diagram that the sem observation of the microporous membrane prepared with traditional annealing methods arrives；
The microcellular structure schematic diagram that the sem observation of the microporous membrane that Fig. 2-5 is prepared for method for annealing of the present invention arrives.
Detailed description of the invention
Embodiment one
Single screw extrusion machine is respectively set as 170 DEG C along hopper to 5 sections of temperature of mouth die from machine barrel, 200 DEG C, 230 DEG C, 240 DEG C, 235 DEG C, with the screw speed of 40rpm, isotactic polypropylene (iPP) is obtained prefabricated membrane with single screw extrusion machine via slit-type die extrusion, carry-over pinch rolls are set as 120 DEG C, and draw ratio is 25.It is placed in the baking oven of 140 DEG C by gained prefabricated membrane high annealing 1h.By electronics universal material experimental machine at 25 DEG C, with the rate of extension of 60mm/min, by the prefabricated membrane cold stretch 40% after annealing.Again by electronics universal material experimental machine at 75 DEG C, with the strain rate of 30mm/min, by the prefabricated membrane hot-stretch 40% after annealing.Finally keep clamp position, heat fixation 10min at 120 DEG C, namely obtain microporous polypropylene membrane prepared by conventional dry.
Adding up the microporous membrane size of microporous membrane with particle diameter statistical software, characterize the moisture-vapor transmission of microporous membrane with rate of perviousness detector, survey the porosity characterizing microporous membrane with dampening, result is all listed in table 1；By the pore structure of sem observation microporous membrane, result is as shown in Figure 1.
Embodiment two
Single screw extrusion machine is respectively set as 170 DEG C along hopper to 5 sections of temperature of mouth die from machine barrel, 200 DEG C, 230 DEG C, 240 DEG C, 235 DEG C, with the screw speed of 40rpm, by isotactic polypropylene (iPP) single screw extrusion machine, obtaining prefabricated membrane via slit-type die extrusion, carry-over pinch rolls are set as 120 DEG C, and draw ratio is 25.Gained prefabricated membrane is placed on process annealing 24h in the baking oven of 50 DEG C.High annealing 1h in again the prefabricated membrane after process annealing being applied the pretightning force of 1N～2N along crystalline region differently-oriented directivity and is placed on the baking oven of 140 DEG C.By electronics universal material experimental machine at 25 DEG C, with the rate of extension of 60mm/min, by the prefabricated membrane cold stretch 40% after annealing.Again by electronics universal material experimental machine at 75 DEG C, with the strain rate of 30mm/min, by the prefabricated membrane hot-stretch 40% after annealing.Finally keep clamp position, heat fixation 10min at 120 DEG C, namely obtain the microporous polypropylene membrane using Novel disk withdrawal ignition method to prepare.
Test sample preparation condition and performance test methods are all with embodiment one, shown in result such as table 1 and accompanying drawing 2.
Embodiment three
Single screw extrusion machine is respectively set as 170 DEG C along hopper to 5 sections of temperature of mouth die from machine barrel, 200 DEG C, 230 DEG C, 240 DEG C, 235 DEG C, with the screw speed of 40rpm, by isotactic polypropylene (iPP) single screw extrusion machine, obtaining prefabricated membrane via slit-type die extrusion, carry-over pinch rolls are set as 120 DEG C, and draw ratio is 25.Gained prefabricated membrane is placed on process annealing 24h in the baking oven of 60 DEG C.High annealing 1h in again the prefabricated membrane after process annealing being applied the pretightning force of 1N～2N along crystalline region differently-oriented directivity and is placed on the baking oven of 140 DEG C.By electronics universal material experimental machine at 25 DEG C, with the rate of extension of 60mm/min, by the prefabricated membrane cold stretch 40% after annealing.Again by electronics universal material experimental machine at 75 DEG C, with the strain rate of 30mm/min, by the prefabricated membrane hot-stretch 40% after annealing.Finally keep clamp position, heat fixation 10min at 120 DEG C, namely obtain the microporous polypropylene membrane using Novel disk withdrawal ignition method to prepare.
Test sample preparation condition and performance test methods are all with embodiment one, shown in result such as table 1 and accompanying drawing 3.
Embodiment four
Single screw extrusion machine is respectively set as 170 DEG C along hopper to 5 sections of temperature of mouth die from machine barrel, 200 DEG C, 230 DEG C, 240 DEG C, 235 DEG C, with the screw speed of 40rpm, by isotactic polypropylene (iPP) single screw extrusion machine, obtaining prefabricated membrane via slit-type die extrusion, carry-over pinch rolls are set as 120 DEG C, and draw ratio is 25.Gained prefabricated membrane is placed on process annealing 24h in the baking oven of 70 DEG C.High annealing 1h in again the prefabricated membrane after process annealing being applied the pretightning force of 1N～2N along crystalline region differently-oriented directivity and is placed on the baking oven of 140 DEG C.By electronics universal material experimental machine at 25 DEG C, with the rate of extension of 60mm/min, by the prefabricated membrane cold stretch 40% after annealing.Again by electronics universal material experimental machine at 75 DEG C, with the strain rate of 30mm/min, by the prefabricated membrane hot-stretch 40% after annealing.Finally keep clamp position, heat fixation 10min at 120 DEG C, namely obtain the microporous polypropylene membrane using Novel disk withdrawal ignition method to prepare.
Test sample preparation condition and performance test methods are all with embodiment one, shown in result such as table 1 and accompanying drawing 4.
Embodiment five
Single screw extrusion machine is respectively set as 170 DEG C along hopper to 5 sections of temperature of mouth die from machine barrel, 200 DEG C, 230 DEG C, 240 DEG C, 235 DEG C, with the screw speed of 40rpm, by isotactic polypropylene (iPP) single screw extrusion machine, obtaining prefabricated membrane via slit-type die extrusion, carry-over pinch rolls are set as 120 DEG C, and draw ratio is 25.Gained prefabricated membrane is placed on process annealing 24h in the baking oven of 80 DEG C.High annealing 1h in again the prefabricated membrane after process annealing being applied the pretightning force of 1N～2N along crystalline region differently-oriented directivity and is placed on the baking oven of 140 DEG C.By electronics universal material experimental machine at 25 DEG C, with the rate of extension of 60mm/min, by the prefabricated membrane cold stretch 40% after annealing.Again by electronics universal material experimental machine at 75 DEG C, with the strain rate of 30mm/min, by the prefabricated membrane hot-stretch 40% after annealing.Finally keep clamp position, heat fixation 10min at 120 DEG C, namely obtain the microporous polypropylene membrane using Novel disk withdrawal ignition method to prepare.
Test sample preparation condition and performance test methods are all with embodiment one, shown in result such as table 1 and accompanying drawing 5.
The extrusion that MD direction is prefabricated membrane in accompanying drawing and draw direction.
The performance (being standard deviation in bracket) of table 1 microporous membrane
As shown in Table 1, the microporous membrane prepared with Novel disk withdrawal ignition method is obviously improved in hole dimension, porosity and moisture-vapor transmission three than the microporous membrane prepared with traditional annealing methods.Particularly noteworthy be moisture-vapor transmission this most intuitively characterize the parameter of microporous membrane serviceability, the microporous membrane of embodiment five preparation is about three times of the steam percent of pass of the microporous membrane of embodiment one preparation.Additionally, comparative example two is to embodiment five it is found that when using the present invention to prepare microporous polypropylene membrane, increase low-temperature anneal temperature and can improve the hole dimension of microporous polypropylene membrane, porosity and moisture-vapor transmission.Particularly when 70 DEG C and 80 DEG C during process annealing, the porosity of the microporous membrane of embodiment four and embodiment five and moisture-vapor transmission have the rising of a saltatory compared with other samples.
The electron scanning micrograph of microporous membrane prepared by different annealing conditions in contrast accompanying drawing 1 and accompanying drawing 2-5, the porosity and the hole dimension that not only demonstrate the microporous membrane that microporous membrane prepared by the Novel disk withdrawal ignition method that table 1 points out is prepared compared with traditional annealing methods have the trend dramatically increased, also demonstrate when using Novel disk withdrawal ignition method simultaneously, the porosity of microporous membrane and hole dimension with low-temperature anneal temperature and increase.It addition, Novel disk withdrawal ignition method can also be obviously improved micropore distribution situation, increase micropore quantity.And along with the increase of low-temperature anneal temperature, the micropore quantity showed increased of microporous membrane, the distribution of micropore is more uniform.
Result above shows, the double annealing method of the present invention can significantly improve the porosity of microporous membrane compared with traditional method for annealing, hole dimension, hole number think the degree that is evenly distributed in hole, thus improving the moisture-vapor transmission of microporous membrane.Additionally, in the present invention, the adjustment to porosity, hole dimension, hole number, the degree that is evenly distributed in hole and moisture-vapor transmission can be realized by the temperature that controls in process annealing process.
Claims (1)
1. a microporous polypropylene membrane method for annealing, it is characterised in that comprise the following steps:
Step one: the polypropylene prefabricated membrane that degree of orientation is 3%～80% of the crystalline region prepared by extrusion curtain coating forming method is placed on process annealing 6～24h in the baking oven at the arbitrary temperature in 50 DEG C to 80 DEG C temperature ranges；
Step 2: the prefabricated membrane after process annealing carries out high annealing immediately, while prefabricated membrane is carried out high annealing, prefabricated membrane after process annealing is applied 1N～2N pretightning force by crystalline region differently-oriented directivity, and is placed in the baking oven of 130～140 DEG C high annealing 40min～1h.
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| CN101695869B (en) * | 2009-10-30 | 2012-05-30 | 沧州明珠塑料股份有限公司 | Preparation method of polyolefin microporous film |
| WO2012105661A1 (en) * | 2011-02-03 | 2012-08-09 | 東レ株式会社 | Porous polypropylene film, separator for electricity storage device, and electricity storage device |
| CN102729532B (en) * | 2012-06-11 | 2015-07-01 | 达尼特材料科技（芜湖）有限公司 | Multilayer porous membrane and preparation method thereof |
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