CN1195008C - Microporous teflon membran and its preparing process - Google Patents
Microporous teflon membran and its preparing process Download PDFInfo
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- CN1195008C CN1195008C CNB021088500A CN02108850A CN1195008C CN 1195008 C CN1195008 C CN 1195008C CN B021088500 A CNB021088500 A CN B021088500A CN 02108850 A CN02108850 A CN 02108850A CN 1195008 C CN1195008 C CN 1195008C
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Abstract
The present invention relates to a microporous teflon film and a preparation method thereof. The weight proportion of dispersed teflon resin and arylhydrocarbon-removel isoparaffin is 100: 20 to 40, the dispersed teflon resin and the arylhydrocarbon-removel isoparaffin are firstly put at the temperature of 100 to 200 DEG C to completely eliminate a lubricating addition agent before longitudinal stretching of a broad band, the transverse biaxial stretching is carried out under the control of a computer, and the microporous film biaxially stretched is put under the temperature of 250 to 400 DEG C to be formed in a hot way. All work procedures of the preparation method are carried out below the thermal decomposition temperature of the teflon resin, the harmful gas generation during the production process can be completely avoided, the preparation method not only guarantees the safe production but also basically reaches to the requirements for environmental protection, and the preparation method simultaneously improves the quality of products and production efficiency.
Description
Technical field
The present invention relates to the improvement of microporous teflon membran manufacture method.
Background technology
Microporous teflon membran making method complexity, operation are long, influence factor is many, thereby will produce high-quality product in enormous quantities and face many problems, lower molecular weight PTFE, and intensity is low, and the tensile percentage of open area is little.And high-molecular weight polymer intensity is good, the porosity height.But perfluorination straight chain polymer weight polymers particle is big, the fusing point height, and melt viscosity is big, and its microporous membrane manufacture method is unconventional processing method.As make the pleurodiaphragmatic in terspace material and select, when making blank, high molecular PTFE to select the proper lubrication auxiliary agent, it and high polymers are through stirring, can form even paste shape material after the extruding so that calendering formation, when longitudinal stretching formed the broadband of fibrous tissue, lubricating auxiliary agent wherein should be removed totally easily.And the emulsification lubricity good be good with paraffin oil, but paraffin oil boiling point height, volatility is little, needs just can remove under the comparatively high temps clean.Also have and select aviation kerosene, it also contains arene except the volatility difference, and the volatilization of phenyl ring thing pollutes workshop condition; Be that the PTFE film if occurrence temperature is out of control, then can produce serious thermolysis in meeting thermolysis more than 415 ℃ when machine-shaping again, when aerobic exists, can produce utmost point poisonous substance---fluorophosgene, it directly endangers operator's health, even life security.As when the PTFE film is stretched, the high more membrane porosity of draft temperature is big more, avoids again but the elongation temperature is higher than the thermolysis that causes more than 415 ℃ as far as possible, and this is a pair of contradiction that pins down mutually; Be will be after the PTFE film stretches in addition through heat setting type, be that high temperature sintering is handled, the shape of film and porosity are just stable, thermal treatment temp generally is controlled at 360 ℃～390 ℃, but PTFE microporous membrane heat setting type effect when being higher than 500 ℃ is better, the thermolysis that this just causes PTFE again produces harmful poisonous gas contaminate environment.CN1193060A also proposes to expand the typing better effects if at 1000～1500 ℃, also thinks high-temperature shaping more than ten times, the film strength height, and the aperture is stable.The method of this ultrahigh-temperature expansion typing is difficult to control in production practice.Therefore, in the production process of PTFE microporous membrane, improve the quality of products, enhance productivity and keep the safety in production, protect the problem of environment coordination, press for solution.
Summary of the invention
The objective of the invention is the problem that exists in the production process at above-mentioned PTFE microporous membrane, seek a kind of prescription and the processing method that can produce high-quality product at a lower temperature, to reach the assurance quality product, enhance productivity, guarantee production safety and purpose free from environmental pollution.
The present invention adopts following technical scheme to realize above-mentioned target.
The manufacture method of microporous teflon membran is characterized by:
A, with pulverous teflon resin with make lubricating auxiliary agent take off the aromatic hydrocarbon isoparaffin by 100:20～40 weight are mixed, stirring and emulsifying, apply 5.88～7.84MPa pressure at 80～100 ℃ then, be pressed into blank in advance;
B, described blank is applied the pressure of 7.84～9.80MPa under 80～100 ℃ of temperature, be pressed into the long broadband of 200～300cm in advance;
C, place 100～200 ℃ the lubricating auxiliary agent in broadband to be removed clean in described broadband;
D, with described broadband in 200～280 ℃ behind the longitudinal stretching, place normal temperature laboratory to place 1～10 day;
E, by computer control cross directional stretch down, temperature is controlled between 100～150 ℃, draw speed is controlled at 6～14 meters/minute, it is 1～1.8m that base band is carried out two-way stretch to width, thickness is 30～60 μ m;
F, the microporous membrane that will stretch place 250～400 ℃ earlier, with 6～14 meters/minute speed heat setting type, again through-10 ℃～10 ℃ cooling curings;
The number-average molecular weight of described teflon resin is 1000～1,400 ten thousand, granularity is that 475～500 μ m, proportion are 2.15～2.16; Taking off the aromatic hydrocarbon isoparaffin is ISOPAR H～M.
The remarkable advantage of technique scheme has two, the aromatic hydrocarbon isoparaffin that takes off of first select tape side chain is made lubricant emulsifier, can mix with PTFE emulsification and form the good cream pasty state blank of plasticity, be convenient to roll into the long broadband of 300cm, be convenient to heated volatile again, the high boiling aromatic hydrocarbon isoparaffin lubricant that takes off is removed totally fully.Foreshortening to originally more than 1/20 on time of drying than aviation kerosene, proportioning amount ratio aviation kerosene reduces more than 20%.Enhance productivity, reduce production costs, also improved the microporous membrane quality, also got rid of of the pollution of fragrant hydrocarbon-benzene complexes species simultaneously workshop and environment; They are two years old, be to have reduced the position to stretch temperature with heat setting type, improve the quality of microporous membrane again, owing to take off aromatic hydrocarbon isoparaffin and the polymer PTFE effect of molecular bond energy each other, the porosity that temperature all can be controlled in microporous membrane below 300 ℃ in drawing process all has more than 85%, ℃ also can not cause the thermolysis of PTFE at heat setting type heat temperature raising to 400, the tensile strength of film and aperture shape are all very stable.
The technical program is through the checking repeatedly of Workshop Production, shows in the computer control production safety that goes to the workshop reliably, and constant product quality can realize production in enormous quantities PTFE microporous membrane.
Preferred forms and embodiment describe
Embodiment one:
1, starting material are selected: tetrafluoroethylene is selected the dispersion type resin powder for use, number-average molecular weight is 1,000 ten thousand～1,400 ten thousand, granularity is 475～500 μ m (ASTMD1457 assay methods), proportion is 2.15～2.16 (JIS-K6891 assay methods), volume density is 500～540g/l (a JIS-K6891 assay method), extrusion pressure is 2.0～2.3 relatively, maximum Pressure reducing ratio is 300～500, tensile strength is 39～40MPa, take off the aromatic hydrocarbon isoparaffin and select ISIPAR H～M for use, initial boiling point is 179 ℃～223 ℃, 187 ℃～254 ℃ of full boiling points, flash-point are 53 ℃～92 ℃, and evaporation rate is less than 10% relatively, aniline point is 84 ℃～89 ℃, and aromatic hydrocarbon content is less than 0.01 weight percent.
2, microporous membrane blank preparation: after satisfactory tetrafluoroethylene dehydrated, with the satisfactory aromatic hydrocarbon isoparaffin that takes off be 100: 30 mixed by weight, stirring and emulsifying.
3, technological process summary:
A, the resin blank after the emulsification is applied 5.88～7.84MPa pressure at 80～100 ℃, be pressed into blank in advance;
B, under 80～100 ℃ of temperature, apply 7.84～9.80MPa pressure, be pressed into the long broadband of 200～300cm;
C, in 100～200 ℃ that the removal of the lubricating auxiliary agent in the broadband is clean;
D, in 200～280 ℃ with the broadband longitudinal stretching, make it produce the base band of fibrous tissue;
E, place normal temperature laboratory to place 1～10 day base band, to eliminate the internal stress of fibrous tissue;
F, by computer control cross directional stretch down, temperature is controlled between 100～150 ℃, draw speed is controlled at 6～14 meters/minute, it is 1～1.8m that base band is carried out two-way stretch to width, thickness is 30～60 μ m;
G, the microporous membrane that will stretch place 250～400 ℃ earlier, with 6～14 meters/minute speed heat setting type, again through-10 ℃～10 ℃ cooling curings.
4, computer control process summary: in the above-mentioned technology, except will removing internal stress in lubricant in the broadband and the broadband totally, be exactly will be to the temperature of cross directional stretch, draw speed, the thickness of film etc. is controlled immediately, for making precise control reliable, employing photovoltaic effect device combines the temperature control of finishing instant variation with computer, on the expanding production line, be provided with more than 2600 infrared heater, and the fluorescent tube of respective numbers, 3 cameras and 6 cover computer control circuit and electric control boxes thereof.When the PTFE of progressively horizontal two-way expansion film process streamline, the weak strong signal input pick up camera that the thickness of film produces light, the signal that camera is collected compares with the thickness of the interval operating and setting film of crossing, arithmetic processing system sends control signal and is fed to electric control box, this information in time is sent to more than 2600 hot spot, hot spot adopt thermal inertia minimum add heat, only need moment just to change heated condition, thereby the uniform thickness of microporous membrane is improved, the gauge control of film is at 30～50 microns, and percentage of open area is stablized about 90%.
5, the microporous membrane performance index of aforesaid method making are: vapor transfer rate is 11000g/m
2D, resistance to hydrostatic pressure is 6000mm, Air permenbility is less than 0.3ml/cm
2S, porosity is greater than 85%, membrane pore size 0.2 μ m～0.3 μ m, 1～1.8 meter of the width of film, film thickness 30～50 μ m, use temperature scope-150～250 ℃.
Company is with reference to PTFE film industry standard (ZBG33004-85) control quality product, and product is through national cotton textiles quality supervision and test center and the SGS of Hong Kong Tongbiao Standard Technology Service Co., Ltd detected result, and many index performances are higher than industry standard.Wherein the monitoring our company in porosity and aperture has adopted the former seed microscopy of AFM to survey instrument and has done the production line detection.
Embodiment two, under starting material selection, raw material ratio, technological process and computer control same case, tetrafluoroethylene and take off of the influence of the different proportionings of aromatic hydrocarbon isoparaffin L relatively emphatically to quality product and yield rate.Experimental result sees Table 1
The different proportionings of table 1 are to microporous membrane quality and yield rate influence
| PTFE：ISOPAR.L (wt) | 20 | 25 | 30 | 35 |
| Vapor transfer rate (g/m 224h) | ＞10000 | ＞11000 | ＞11000 | ＞10000 |
| Water pressure resistance (mm) | 3000 | 5000 | 6000 | 4000 |
| Uniform thickness (μ m) | 20～80 | 30～60 | 30～50 | 30～60 |
| Porosity (%) | 85 | ＞85 | ＞85 | 85 |
| Yield rate (%) | 85 | 90 | 98 | 85 |
| Product hierarchy | Goods of inferior quality | Acceptable end product | Acceptable end product | Third grade product |
The above results shows, the tetrafluoroethylene dispersion type resin is 100: 25～30 weight with the best proportioning of taking off aromatic hydrocarbon isoparaffin L, and in this ratio range, each procedure operation is all smooth, thereby the quality of product and yield rate are all than higher.
Embodiment three: select at starting material, raw material ratio, under technological process and the computer control same case, focus on more different lubricants, under differing temps, automatic evaporable time from broadband of the same area, correlated lubricant is 25: 100 for the part by weight of solvent oil (as aviation kerosene) commonly used and ISOPAR.L (isoparaffin L) they and PTFE powdex.The results are shown in Table 2.
Table 2 lubricant volatilization time ratio
| Drying temperature | Take off aromatic hydrocarbon isoparaffin L utility time (hour) | The aviation kerosene utility time (hour) |
| 0～10℃ | 24×4 | 24×35 |
| 10～25℃ | 24×2 | 24×25 |
| 25～40℃ | 24×1 | 24×20 |
As known from Table 2, when the PTFE blank is made the broadband bar, adopt and to take off aromatic hydrocarbon isoparaffin lubricant and will remove that it is more much easier than aviation kerosene, the consumption that takes off the aromatic hydrocarbon isoparaffin also reduces 20% than aviation kerosene consumption.This is effectively way of raising labour productivity to Workshop Production in enormous quantities, and this pollutes workshop and environment to reducing the benzene class certainly, guarantees production safety and personnel health, also is very favorable.Employing is taken off the aromatic hydrocarbon isoparaffin and made lubricant, can stretch at a lower temperature and the heat setting type processing, avoids the thermolysis effect of PTFE fully, and is very favourable to environment protection and production safety.In the trial production of PTFE microporous membrane production plant of the present invention, reach basically and improve the quality of products and yield rate and production safety and purpose free from environmental pollution.
Claims (4)
1, the manufacture method of microporous teflon membran is characterized by:
A, with pulverous teflon resin with do lubricating auxiliary agent take off the aromatic hydrocarbon isoparaffin by 100: 20～40 weight mix, stirring and emulsifying, apply 5.88～7.84MPa pressure at 80～100 ℃ then, be pressed into blank in advance;
B, described blank is applied the pressure of 7.84～9.80MPa under 80～100 ℃ of temperature, be pressed into the long broadband of 200～300cm in advance;
C, place 100～200 ℃ the lubricating auxiliary agent in broadband to be removed clean in described broadband;
D, with described broadband in 200～280 ℃ behind the longitudinal stretching, place normal temperature laboratory to place 1～10 day;
E, by computer control cross directional stretch down, temperature is controlled between 10～150 ℃, draw speed is controlled at 6～14 meters/minute, it is 1～1.8m that base band is carried out two-way stretch to width, thickness is 30～60 μ m;
F, the microporous membrane that will stretch place 250～400 ℃ earlier, with 6～14 meters/minute speed heat setting type, again through-10 ℃～10 ℃ cooling curings;
The number-average molecular weight of described teflon resin is 1000～1,400 ten thousand, granularity is that 475～500 μ m, proportion are 2.15～2.16; Taking off the aromatic hydrocarbon isoparaffin is ISOPAR H～M.
2, the manufacture method of microporous teflon membran as claimed in claim 1 is characterized in that number-average molecular weight is that 1000～1,400 ten thousand teflon resin powder and the proportioning of isoparaffin ISOPAR H～M are 100: 30 weight.
3, the manufacture method of microporous teflon membran as claimed in claim 1 is characterized in that the even molecular weight of number is that 1000～1,400 ten thousand teflon resin powder and the proportioning of taking off aromatic hydrocarbon isoparaffin ISOPAR L are 100: 25 weight.
4, the manufacture method of microporous teflon membran as claimed in claim 1, the temperature that it is characterized in that adopting the photovoltaic effect device to combine and finish instant variation control with computer.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021088500A CN1195008C (en) | 2002-04-14 | 2002-04-14 | Microporous teflon membran and its preparing process |
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| CNB021088500A CN1195008C (en) | 2002-04-14 | 2002-04-14 | Microporous teflon membran and its preparing process |
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| CN1195008C true CN1195008C (en) | 2005-03-30 |
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Cited By (1)
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| CN104369400A (en) * | 2013-08-12 | 2015-02-25 | 浙江舒普氟材科技有限公司 | Production technology of flame retardant polytetrafluoroethylene micropore film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104369400A (en) * | 2013-08-12 | 2015-02-25 | 浙江舒普氟材科技有限公司 | Production technology of flame retardant polytetrafluoroethylene micropore film |
| CN104369400B (en) * | 2013-08-12 | 2016-10-05 | 浙江舒普氟材科技有限公司 | A kind of fire-retardant polytetrafluoroethylmicroporous microporous membrane production technology |
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