CN103451758B - Polytetrafluoroethylene ultrafine fiber - Google Patents

Polytetrafluoroethylene ultrafine fiber Download PDF

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CN103451758B
CN103451758B CN201310423233.8A CN201310423233A CN103451758B CN 103451758 B CN103451758 B CN 103451758B CN 201310423233 A CN201310423233 A CN 201310423233A CN 103451758 B CN103451758 B CN 103451758B
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raw material
cross directional
heat setting
directional stretch
temperature
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CN103451758A (en
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徐志梁
罗文春
姜学梁
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Zhejiang koal theis environmental protection special materials Polytron Technologies Inc
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ZHEJIANG KERTICE HI-TECH FLUOR-MATERIAL Co Ltd
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Abstract

The invention relates to polytetrafluoroethylene ultrafine fiber. The polytetrafluoroethylene ultrafine fiber is prepared by the following method which sequentially comprises the steps of lubricating and mixing, screening, modifying and mixing, extruding, calendering, removing aviation kerosene, stretching, curing and deoiling and breaking a net and is characterized in that silicone oil is added in the modifying and mixing process; when the net is broken, a comb is densified and combing is accelerated, the fiber of 1D and below can be prepared and good physical performances can be kept. The ultrafine fiber can be used for filtering high-temperature flue gas after being made into a needled felt, the filtration flux can be ensured while the interception effect against PM2.5 is very good, and even if the emission quantity is large, the emission quantity of the PM2.5 can be still controlled to be below 10mg/m<3>.

Description

Polytetrafluoroethylsuperfine superfine fiber
Technical field
The present invention relates to a kind of polytetrafluoroethylsuperfine superfine fiber.
Background technology
In view of in air, PM2.5 remains high, and air problem is subject to the attention of compatriots again.PM2.5 mainly comes from burning, especially utilizes coal to carry out the enterprise generated electricity.If it is huge generating set all to be reconstructed obviously investment.A kind of coated filter material is there is in prior art.Coated filter material prepared by full polytetrafluoroethylene (PTFE) has good filter effect, the PM2.5 in flue gas can be retained down.PTFE membrane filter material is that one deck is polytetrafluoroethylene (PTFE) screen cloth casing play, and another layer is the teflon membrane filter sticked thereon usually by double-layer structure.PTFE membrane filter material rejection effect is in the market more than 99%.But the flux of coated filter material is low, and namely filter efficiency is poor.If coated filter material to be used for the smoke stack emission mouth in thermal power plant, then very likely there is the situation of booster, there is serious potential safety hazard.A kind of Nomex is also there is in prior art, but due to technical reason, not yet prepare the Nomex of full polytetrafluoroethylene (PTFE), the Nomex of other materials, as terylene needled felt, be not suitable for the process to high-temperature flue gas, and the rejection effect of this Nomex is also undesirable, PM2.5 discharge capacity reaches 50mg/m 3.Nomex is a kind of special construction of nonwoven fabric, is on special base material, adopt needing machine superfine fibre acupuncture to be made on special base material.Have dacron ultrafine fiber in prior art, but the difficulty of processing of polytetrafluoroethylene (PTFE) is large, not yet prepares the superfine fibre of polytetrafluoroethylene (PTFE).The thinnest polytetrafluoroethylene fibre can prepared in prior art is at about 5D, and the fiber required for Nomex that preparation has good filter effect needs to be low to moderate 1D.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of polytetrafluoroethylsuperfine superfine fiber.
The scheme that the present invention solves the problems of the technologies described above is as follows:
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching to while raw material band removing aviation kerosine, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 1% ~ 10%/s, draw ratio 2 ~ 6, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 45 ~ 50mm/s first, draw ratio 20 ~ 25, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 180 ~ 200 times, rate of extension 20 ~ 30 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 50 ~ 100%, and described quickening is specially quickening 50 ~ 200%.
Preferred as technique scheme, the addition of described aviation kerosine is 10 ~ 30% of ptfe micropowder quality.
Preferred as technique scheme, the addition of described silicone oil is 1 ~ 10% of ptfe micropowder quality.
Preferred as technique scheme, the particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm.
The selected aviation kerosine of the present invention, as lubricating oil, makes ptfe micropowder to be removed better by mixed, processed, lubricating oil better.Such as adopt aviation kerosine to have worse detachability than gasoline, but have better calenderability; Than diesel oil, there is better detachability.The quality of the raw material band quality that described calenderability rolls out after referring to and entering calendaring processes.The quality of raw material band quality has following standard: as the even performance of tensile property, stretching, raw material band the even performance of thickness, draw high after the intensity etc. of raw material band.
After superfine fibre makes Nomex, examine under a microscope, Nomex surface can form fine hair shape, improves its interdiction capability to PM2.5 significantly.And dacron ultrafine fiber heat resistance is poor, under the temperature impact of high-temperature flue gas, the fine hair on surface can deform, and then affects its interdiction capability.And the C-F bond of polytetrafluoroethylmaterial material is closed very firm, and fluorine atom gets up the carbon atom shielding on main chain, and therefore, polytetrafluoroethylmaterial material has the resistant to elevated temperatures ability of very strong acid-fast alkali-proof.But to be also it be difficult to processed reason for this, because polytetrafluoroethylene (PTFE) participates in the poor ability of chemical reaction, it is again linear molecule, the intermolecular ability of entwining is also very low, therefore polytetrafluoroethylene (PTFE) ethene is difficult to make superfine fibre by spin processes, even if it is also very low to process its intensity, industrially cannot to use.Therefore extension can only be adopted, and current extension can only accomplish about 5D.Therefore, polytetrafluoroethylsuperfine superfine fiber be prepared, will manufacture can by La get evenly, thinner after, TENSILE STRENGTH can continue maintain; And comb encryption to be stood and the polytetrafluoroethylraw raw material band of combing speed acceleration process.This just proposes new requirement to its toughness.The present inventor improves tensile property and the intensity of raw material band significantly after with the addition of silicone oil in the feed, after making stretching make film, this film can encrypted combing and accelerate combing and constantly when scoring a goal, and remains good fracture strength.Also therefore, at equipment in the past after transformation, 1D and following polytetrafluoroethylsuperfine superfine fiber can be produced.The Nomex that 1D and following polytetrafluoroethylene fibre are produced not only has good flux, good heat resistanceheat resistant performance, also has good strainability, and obviously can reduce the content of PM2.5 in discharge flue gas, PM 2.5 discharge capacity is at 10mg/m 3below.
Compared with the polytetrafluoroethylfiber fiber film that finished film of the present invention and prior art are obtained, there is thinner characteristic, and TENSILE STRENGTH to double left and right than the stretched polytetrafluoroethylene intensity of prior art.The filtration of high-temperature flue gas can be used for after this superfine fibre makes Nomex, guarantee filtration flux while, very good to the interception result of PM2.5, though discharge capacity large more also can control PM2.5 discharge capacity at 10mg/m 3below.
In sum, the present invention has following beneficial effect:
The polytetrafluoroethylfiber fiber film that the present invention obtains has better toughness, can be drawn thinner evenly, can stand when scoring a goal comb encryption and accelerate process.Thus, polytetrafluoroethylfiber fiber film of the present invention can prepare superfine fibre.This superfine fibre, after making Nomex, effectively can solve the problem of PTFE coated filter material in prior art, and the problem of dacron ultrafine fiber Nomex in prior art, can by the fume emission of coal-fired power plant, and control PM 2.5 discharge capacity is at 10mg/m 3below.
Detailed description of the invention
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the amendment not having creative contribution as required after reading this description, as long as but be all subject to the protection of Patent Law in right of the present invention.
Embodiment one
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 10% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 1% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 1%/s, draw ratio 2, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 45mm/s first, draw ratio 20, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 180 times, rate of extension 20 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Described finished film elongation at break 30%, TENSILE STRENGTH 10Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 50%, and described quickening is specially quickening 50%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment two
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 13% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 2% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 2%/s, draw ratio 2, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 45mm/s first, draw ratio 20, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 182 times, rate of extension 21 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 30%, TENSILE STRENGTH 10Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 50%, and described quickening is specially quickening 60%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment three
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 16% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 3% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 13%/s, draw ratio 3, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 46mm/s first, draw ratio 21, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 184 times, rate of extension 22 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 30%, TENSILE STRENGTH 10Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 60%, and described quickening is specially quickening 70%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment four
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 19% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 4% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 4%/s, draw ratio 3, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 46mm/s first, draw ratio 21, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 186 times, rate of extension 23mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 31%, TENSILE STRENGTH 10.2Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 60%, and described quickening is specially quickening 80%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment five
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 22% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 5% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 5%/s, draw ratio 4, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 47mm/s first, draw ratio 22, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 188 times, rate of extension 24 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 32%, TENSILE STRENGTH 10.2Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 70%, and described quickening is specially quickening 90%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment six
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 25% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 6% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 6%/s, draw ratio 4, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 47mm/s first, draw ratio 22, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 188 times, rate of extension 25 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 32%, TENSILE STRENGTH 10.5Mpa.;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 70%, and described quickening is specially quickening 100%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment seven
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 28% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 7% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 7%/s, draw ratio 5, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 48mm/s first, draw ratio 23, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 192 times, rate of extension 26mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 32%, TENSILE STRENGTH 10.3Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 80%, and described quickening is specially quickening 110%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment eight
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 31% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 8% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 8%/s, draw ratio 5, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 48mm/s first, draw ratio 23, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 192 times, rate of extension 27mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 30%, TENSILE STRENGTH 10Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 80%, and described quickening is specially quickening 120%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment nine
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 34% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 9% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 9%/s, draw ratio 6, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 49mm/s first, draw ratio 24, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 196 times, rate of extension 28 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 30%, TENSILE STRENGTH 10Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 90%, and described quickening is specially quickening 130%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment ten
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 37% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 10% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 10%/s, draw ratio 6, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 49mm/s first, draw ratio 24, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 196 times, rate of extension 29 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 30%, TENSILE STRENGTH 10Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 90%, and described quickening is specially quickening 140%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Embodiment 11
Polytetrafluoroethylsuperfine superfine fiber, be made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing; The addition of described aviation kerosine is 40% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix; The addition of described silicone oil is 10% of ptfe micropowder quality;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching while described aviation kerosine is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 10%/s, draw ratio 6, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 50mm/s first, draw ratio 25, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 200 times, rate of extension 30 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film; Elongation at break 30%, TENSILE STRENGTH 10Mpa;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 100%, and described quickening is specially quickening 150%.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
Comparative example
1. mix: in ptfe micropowder, be mixed into low surface tension lubricating oil, addition is 10% of ptfe micropowder quality; The particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm;
2. sieve: with 10 ~ 30 mesh sieves, above-mentioned batch mixing is sieved;
3. preformed: lower 20 hours of the temperature batch mixing through screening being placed in 20 DEG C;
4. extrude: use extruder to be extruded by above-mentioned preformed raw material, squeezing parameter is as follows, extruded velocity 5mm/min, extrudes diameter 15mm, and membrana oralis draw ratio L/D is 20, cone angle 30 °, compression ratio 140;
5. roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 DEG C; Obtained raw material band;
6. except lubricant: to described raw material band drying process 18 hours at the temperature of the boiling point of a little higher than described low surface tension lubricating oil, remove described low surface tension lubricating oil;
7. drawing and setting: carry out longitudinal stretching while described low surface tension lubricating oil is removed to raw material band, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, obtained miillpore filter after three HEAT SETTING; During drawing and setting, controling parameters is as follows;
8. score a goal, conventional comb density, conventional speeds scores a goal.
The technological parameter of drawing and setting step is as follows: longitudinal stretching speed 1%/s, longitudinal stretching multiple 2, heat setting temperature 200 DEG C, cross directional stretch speed 10mm/s first, cross directional stretch multiple 2 first, second heat setting temperature 200 DEG C, again cross directional stretch speed 40mm/s, cross directional stretch multiple 50 again, three heat setting temperatures 250 DEG C.
The elongation at break 10%, TENSILE STRENGTH 5Mpa of obtained film.
The computational methods of elongation at break are as follows:
Elongation at break=△ L/L 0* 100%;
(former long L 0, under axial tension effect, the breaking length after distortion is L, so extension at break △ L=L-L 0)
The computational methods of TENSILE STRENGTH are as follows: σ t=p/(b × d)
σ t is TENSILE STRENGTH (MPa); P is peak load (N); B is specimen width (mm); D is sample thickness (mm).
The fiber of comparative example the most carefully can reach 3D, but more than 80% all at more than 5D.
The fibre fineness of embodiment one ~ 11 is substantially all at about 1D, and CV value is little.Namely CV value fluctuates one and is worth, in order to represent the stability of product.

Claims (5)

1. polytetrafluoroethylsuperfine superfine fiber, is characterized in that, represents that the dawn number of chemical fibre fineness is at below 1D, is specifically made up of following methods:
(1) lubrication mixing: add aviation kerosine in ptfe micropowder, mixing;
(2) sieve: sieve with 10 ~ 30 mesh sieves;
(3) modification mixing: add silicone oil again, then mix;
(4) extrude: use extruder to be extruded by the raw material that modification mixes, squeezing parameter is as follows, extruded velocity 5 ~ 15mm/min, extrudes diameter 15 ~ 25mm, and die entrance angle L/D is 20 ~ 40, cone angle 30 ~ 50 °, compression ratio 140 ~ 160;
(5) roll: use calender to roll the raw material after extruding, during calendering, roller temperature controls is 140 ~ 180 DEG C, obtained raw material band;
(6) except boat coal: to described raw material band drying process 18 ~ 24 hours at the temperature of the boiling point higher than described aviation kerosine, remove described aviation kerosine;
(7) stretch: carry out longitudinal stretching to while raw material band removing aviation kerosine, then carry out a HEAT SETTING; Then carry out cross directional stretch first, second heat is shaped, cross directional stretch again, three HEAT SETTING, obtained polytetrafluoroethylfiber fiber film; During drawing and setting, controling parameters is as follows: longitudinal stretching speed 1% ~ 10%/s, draw ratio 2 ~ 6, heat setting temperature 200 ~ 250 DEG C; Cross directional stretch speed 45 ~ 50mm/s first, draw ratio 20 ~ 25, second heat setting temperature 200 ~ 250 DEG C; Cross directional stretch is redraw 180 ~ 200 times, rate of extension 20 ~ 30 mm/s to the raw material band after cross directional stretch first again, and three heat setting temperatures control to be 250 ~ 300 DEG C, obtain shaping membrane;
(8) solidify de-oiling: the multiple Concourse Division formula process raised gradually in temperature by described shaping membrane, the initial temperature of described sectional type process is 300 ~ 320 DEG C, until described shaping membrane is heated to transparence, obtains finished film;
(9) score a goal: to score a goal process to described finished film, the chi of former comb is buckled encryption by cutting machine, the combing speed of comb is accelerated, and described encryption is specially encryption 50 ~ 100%, and described quickening is specially quickening 50 ~ 150%.
2. polytetrafluoroethylsuperfine superfine fiber according to claim 1, is characterized in that: the addition of described aviation kerosine is 10 ~ 30% of ptfe micropowder quality.
3. polytetrafluoroethylsuperfine superfine fiber according to claim 1 and 2, is characterized in that: the addition of described silicone oil is 1 ~ 10% of ptfe micropowder quality.
4. polytetrafluoroethylsuperfine superfine fiber according to claim 1 and 2, is characterized in that: the particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm.
5. polytetrafluoroethylsuperfine superfine fiber according to claim 3, is characterized in that: the particle diameter of selected ptfe micropowder is 0.215 ~ 0.225 μm.
CN201310423233.8A 2013-09-17 2013-09-17 Polytetrafluoroethylene ultrafine fiber Active CN103451758B (en)

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Patentee after: Zhejiang koal theis environmental protection special materials Polytron Technologies Inc

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Denomination of invention: Polytetrafluoroethylene Microfiber

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