CN105885081A - Plasma modification method for polytetrafluoroethylene microporous membrane - Google Patents

Plasma modification method for polytetrafluoroethylene microporous membrane Download PDF

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Publication number
CN105885081A
CN105885081A CN201610214479.8A CN201610214479A CN105885081A CN 105885081 A CN105885081 A CN 105885081A CN 201610214479 A CN201610214479 A CN 201610214479A CN 105885081 A CN105885081 A CN 105885081A
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Prior art keywords
microporous membrane
plasma
modification method
teflon membran
microporous teflon
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CN201610214479.8A
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CN105885081B (en
Inventor
杨加志
夏庆成
毛霏
韩静
刘晓慧
曾干敏
孙东平
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a plasma modification method for a polytetrafluoroethylene microporous membrane. A low temperature plasma treatment method is adopted for conducting surface modification on the PTFE microporous membrane, process parameters of low-temperature plasma treatment, such as the low-temperature plasma gas type, the treatment distance, the radio-frequency power, the treatment time and the gas circulation volume, are controlled, hydrophilia of the PTFE microporous membrane is improved, the PTFE microporous membrane which is originally quite great in hydrophobicity is modified into the PTFE microporous membrane which is quite great in hydrophilia, the water contact angle is lowered to approximately 40 degrees from the original approximately 13 degrees, and meanwhile mechanical strength of the PTFE microporous membrane is maintained. The plasma modification method is short in cycle and low in cost, commercialized production can be conducted, and the application scope of the PTFE microporous membrane is further expanded.

Description

A kind of Plasma modification method of microporous teflon membran
Technical field
The invention belongs to the proton exchange membrane material field of fuel cell, be specifically related to a kind of microporous teflon membran etc. Gas ions method of modifying.
Background technology
Politef (PTFE), by tetrafluoroethylene polymerization, comprises only C-C key and C-F chemical bond, two Chemical bond all contains the highest chemical bond energy, and therefore politef chemistry character is highly stable, can be as anticorrosive Material, degradation rate is the least, and service life is long, medical application material, anion exchange membrane, encapsulant, The fields such as filtering material are widely used.
Microporous teflon membran hydrophobicity is strong, and surface can be relatively low, and caking property and wettability are more weak, limits its application, Therefore need to carry out hydrophilically modified to it.[Materials Research Bulletin, 2009,44 (6): 1437-1440] uses Load C eO on PTFE microporous membrane2, Hydrothermal Synthesis CeO2/ PTFE composite film, the method operating process is loaded down with trivial details, Preparation time is long, and modified water contact angle can only achieve 80 °, and modified effect is not ideal enough.【Energy Procedia, 2011,9:539-544] with butyl titanate as raw material, on PTFE microporous membrane, TiO is loaded by hydrothermal synthesis method2, Form TiO2/ PTFE composite micro porous film, the method generated time is longer, and process is the most comparatively laborious, and water contact angle may only Reach 70 °, and the mechanical strength of microporous membrane reduces.[Vacuum, 2012,86 (6): 643-647] uses single argon Gas plasma treatment PTFE film, the contact angle of the film after process is 60 °, and the damage to microporous membrane is relatively big simultaneously, machinery Intensity reduces.[Applied Surface Science, 2008,254 (6): 1614-1621] uses nitrogen plasma to process, and changes The contact angle of the PTFE film after property is 55 °, and the mechanical strength of microporous membrane is declined slightly.
Summary of the invention
In hydrophilic modification method for existing microporous teflon membran, modified effect is the best, modified microporous membrane The deficiency that mechanical strength reduces, the invention provides the Plasma modification method of a kind of microporous teflon membran, uses Low Temperature Plasma Treating method carries out surface modification to PTFE microporous membrane, by controlling the work of Low Temperature Plasma Treating Skill parameter, including low temperature plasma gas kind, processes distance, radio-frequency power, process time and gas circulation, changes The hydrophilic of kind PTFE microporous membrane, becomes, by PTFE microporous modification the strongest for former hydrophobicity, the PTFE that hydrophilic is stronger Microporous membrane, water contact angle is down to about 40 ° by original about 130 °, is kept the mechanical strength of PTFE microporous membrane simultaneously.
Technical scheme is as follows:
The Plasma modification method of a kind of microporous teflon membran, specifically comprises the following steps that
Step 1, the pretreatment of PTFE microporous membrane: PTFE microporous membrane is soaked in acetone soln 12～24h, then Soaking 3～12h in the ethanol solution of 80%-98%, after ethanol solution repeatedly soaks removing acetone, deionized water cleans and removes Ethanol, is finally dried 10～24h at 30～70 DEG C, obtains the PTFE microporous membrane cleaned up；
Step 2, Cement Composite Treated by Plasma: the PTFE microporous membrane cleaned up is placed in plasma fine vacuum preparation room, After evacuation, it is passed through CH4And N2, control CH4And N2Volume ratio be 3:1～1:3, the total flow of gas is 10cm3/ s～50cm3/ s, power is 20w～100w, and process distance is 1cm～100cm, and the process time is 20s～100s, Finally give modified PTFE microporous membrane.
Preferably, in step 2, described CH4And N2Volume ratio be 2:1～1:2, more preferably 1:1.
Preferably, in step 2, the total flow of described gas is 20cm3/ s～40cm3/s。
Preferably, in step 2, described power is 40w～80w.
Preferably, in step 2, described process distance is 20cm～80cm, more preferably 40cm～60cm.
Preferably, in step 2, the described process time is 40s～80s.
Compared with prior art, the present invention has a following remarkable advantage: the present invention use methane and nitrogen mixed gas etc. from PTFE microporous membrane is modified by the method that daughter processes, and modified contact angle can be down to 40 °, significantly improves PTFE The hydrophilic of microporous membrane, maintains the mechanical performance that PTFE microporous membrane is excellent simultaneously.The inventive method cycle is short, cost Cheap, can commercially produce.
Accompanying drawing explanation
Fig. 1 is untreated PTFE microporous membrane (a) and the contacting of PTFE microporous membrane (b) after Cement Composite Treated by Plasma Angle figure.
Fig. 2 is the graph of a relation of plasma power and PTFE microporous membrane contact angle.
Fig. 3 is the graph of a relation of plasma processing time and PTFE microporous membrane contact angle.
Fig. 4 is the ratio graph of a relation with PTFE microporous membrane contact angle of plasma air inlet.
Fig. 5 is the gas flow graph of a relation with PTFE microporous membrane contact angle of plasma treatment air inlet.
Fig. 6 is the graph of a relation of plasma treatment distance and PTFE microporous membrane contact angle.
Fig. 7 is the result figure of the PTFE microporous membrane hot strength test after plasma treatment.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
The pretreatment of PTFE microporous membrane:
PTFE microporous membrane decurl with two A4 folders, is placed under sheet cutter, be cut into several 5 × 5cm PTFE microporous membrane, the PTFE microporous membrane cut is immersed in acetone soln, in fume hood soak 12～24h, Then in the ethanol solution of 80%～98%, soak 3～12h, repeatedly change ethanol solution, remove acetone, then spend big Amount ionized water is cleaned multiple times removing ethanol, is finally putting in vacuum drying oven, is dried under conditions of 30～70 DEG C 10～24h, dried PTFE microporous membrane is cooled to room temperature, then microporous membrane is put and fix on a glass, carry out Next step plasma modification.
Embodiment 2
The preprocess method of PTFE microporous membrane such as embodiment 1.
Cement Composite Treated by Plasma:
First pretreated PTFE microporous membrane is placed in plasma fine vacuum preparation room, at N2+CH4Mixed gas Under, regulation plasma treatment distance is 40cm, and selection processes time 100s, and gas flow selects 20cm3/ s, air inlet Ratio selects 1:1, and the gas flow of namely for methane and nitrogen is all 10cm3/ s, controls plasma power, and power selects respectively Select 20w, 40w, 60w, 80w, 100w.
The PTFE microporous membrane of Cement Composite Treated by Plasma is carried out with JY-82 contact angle instrument (Chengde testing machine factory) respectively Measure, take 6 diverse locations respectively and measure the contact angle of water respectively, finally take its meansigma methods.Contact angle and plasma Process the graph of a relation of power as shown in Figure 2.By Fig. 2 it is recognised that contact angle is between 40 °～60 ° during 20w～100w. From power 20w to the 40w of plasma treatment, contact angle tapers into, and minimizes to contact angle during 40w, contact Angle reaches 42.84 °, and 40w to 100w contact angle starts to become larger.
Embodiment 3
The preprocess method of PTFE microporous membrane such as embodiment 1.
Cement Composite Treated by Plasma:
Pretreated PTFE microporous membrane is placed in plasma fine vacuum preparation room, at N2+CH4Under mixed gas, Regulation plasma treatment distance is 40cm, and gas flow selects 30cm3/ s, aeration ratio selects 1:1, namely for methane and nitrogen The gas flow of gas is all 10cm3/ s, the power of plasma treatment is 40w, controls plasma processing time, and the time divides Not Wei 20s, 40s, 60s, 80s, 100s.
Fig. 1 is untreated PTFE microporous membrane (a) and the contacting of PTFE microporous membrane (b) after Cement Composite Treated by Plasma Angle figure.The graph of a relation of contact angle and plasma treatment time is as shown in Figure 3.It will be seen from figure 1 that plasma treatment Front PTFE film contact angle is 130 °, and the contact angle after final process reaches 40 °.As can be seen from Figure 3, before 20s, Along with the increase of the time of process, contact angle is all to reduce the most rapidly, arrives minimum when 20s, and contact angle is 41.82 °. 20s to 40s slowly becomes big, just trends towards stable after 40s.
Embodiment 4
The preprocess method of PTFE microporous membrane such as embodiment 1.
Cement Composite Treated by Plasma:
Pretreated PTFE microporous membrane is placed in plasma fine vacuum preparation room, at N2+CH4Under mixed gas, Regulation plasma treatment distance is 40cm, and gas flow selects 30cm3/ s, processes power 40w, processes time 20s, Controlling aeration ratio, methane and nitrogen aeration ratio are respectively 3:1,2:1,1:1,1:2,1:3, namely for methane and nitrogen Air inflow is respectively 22.5cm3/ s and 7.5cm3/ s, 20cm3/ s and 10cm3/ s, 15cm3/ s and 15cm3/ s, 10cm3/s And 20cm3/ s, 7.5cm3/ s and 22.5cm3/s。
The graph of a relation of contact angle and aeration ratio is as shown in Figure 4.From fig. 4, it can be seen that after contact angle is a first reduction The process increased, when gas ratio is 1:1, contact angle has reached minimum.
Embodiment 5
The preprocess method of PTFE microporous membrane such as embodiment 1.
Cement Composite Treated by Plasma:
Pretreated PTFE microporous membrane is placed in plasma fine vacuum preparation room, at N2+CH4Under mixed gas, Regulation plasma treatment distance is 40cm, and aeration ratio is 1:1, and plasma treatment time is 20s, at plasma Reason power is 40w, controls gas flow, and total gas flow rate is respectively 10cm3/ s, 20cm3/ s, 30cm3/ s, 40cm3/ s, 50cm3/s。
The graph of a relation of contact angle and total gas flow rate is as shown in Figure 5.As can be seen from Figure 5, become when the gas flow of plasma During change, under certain conditions, contact angle is gradually reduced along with the increase of gas flow, but when gas flow is 20cm3/ s, contact angle arrives minimum 40.83 °, and contact angle starts to increase on the contrary subsequently.
Embodiment 6
The preprocess method of PTFE microporous membrane such as embodiment 1.
Cement Composite Treated by Plasma:
Pretreated PTFE microporous membrane is placed in plasma fine vacuum preparation room, at N2+CH4Under mixed gas, Regulation aeration ratio is 1:1, and plasma treatment time is 20s, and Cement Composite Treated by Plasma power is 40w, plasma treatment Gas flow is 20cm3/ s, control plasma treatment distance, plasma treatment distance respectively 1cm, 20cm, 40cm, 60cm, 80cm, 100cm.
The graph of a relation of contact angle and plasma treatment distance is as shown in Figure 6.As can be seen from Figure 6, plasma treatment distance is from 1cm At 40cm, contact angle shows first increases the trend reduced afterwards, plasma treatment distance 40cm to 100cm contact angle Becoming larger, at 40cm, contact angle minimizes.
Embodiment 7
The preprocess method of PTFE microporous membrane such as embodiment 1.
Cement Composite Treated by Plasma:
Pretreated PTFE microporous membrane is placed in plasma fine vacuum preparation room, at N2+CH4Under mixed gas, Processing power 40w, gas ratio is 1:1, and gas flow is 20cm3/ s, the condition that plasma treatment distance is 40cm Under, controlling plasma treatment time, 20s, 40s, 60s, 80s, 100s carry out Cement Composite Treated by Plasma.To handle well PTFE microporous membrane, take the strip microporous membrane of 2cm × 5cm, (material is newly thought carefully to the hot strength instrument of employing by Shenzhen Material detects company limited's tensile strength tester) carry out hot strength test.Hot strength is with plasma treatment time Graph of a relation, result is as shown in Figure 7.From figure 7 it can be seen that after Cement Composite Treated by Plasma, the stretching of PTFE microporous membrane is strong Degree keeps constant, illustrate that the method for modifying of the present invention mechanical performance on PTFE microporous membrane is without affecting.

Claims (8)

1. the Plasma modification method of a microporous teflon membran, it is characterised in that specifically comprise the following steps that
Step 1, the pretreatment of microporous teflon membran: microporous teflon membran is soaked in acetone soln 12～24h, then in the ethanol solution of 80%-98% soak 3～12h, ethanol solution repeatedly soak removing acetone after, go from Sub-water cleans and removes ethanol, is finally dried 10～24h at 30～70 DEG C, obtains the microporous teflon membran cleaned up；
Step 2, Cement Composite Treated by Plasma: the microporous teflon membran cleaned up is placed in plasma fine vacuum and prepares In room, after evacuation, it is passed through CH4And N2, control CH4And N2Volume ratio be 3:1～1:3, the total flow of gas For 10cm3/ s～50cm3/ s, power is 20w～100w, and process distance is 1cm～100cm, and the process time is 20s～100s, Finally give modified microporous teflon membran.
The Plasma modification method of a kind of microporous teflon membran the most according to claim 1, its feature exists In, in step 2, described CH4And N2Volume ratio be 2:1～1:2.
The Plasma modification method of a kind of microporous teflon membran the most according to claim 1, its feature exists In, in step 2, described CH4And N2Volume ratio be 1:1.
The Plasma modification method of a kind of microporous teflon membran the most according to claim 1, its feature exists In, in step 2, the total flow of described gas is 20cm3/ s～40cm3/s。
The Plasma modification method of a kind of microporous teflon membran the most according to claim 1, its feature exists In, in step 2, described power is 40w～80w.
The Plasma modification method of a kind of microporous teflon membran the most according to claim 1, its feature exists In, in step 2, described process distance is 20cm～80cm.
The Plasma modification method of a kind of microporous teflon membran the most according to claim 1, its feature exists In, in step 2, described process distance is 40cm～60cm.
The Plasma modification method of a kind of microporous teflon membran the most according to claim 1, its feature exists In, in step 2, the described process time is 40s～80s.
CN201610214479.8A 2016-04-07 2016-04-07 A kind of Plasma modification method of microporous teflon membran Expired - Fee Related CN105885081B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114075348A (en) * 2020-08-14 2022-02-22 南京理工大学 Preparation method of polymerized acrylic monomer on polytetrafluoroethylene microporous membrane
CN117146286A (en) * 2023-10-30 2023-12-01 上海朗蔚环保科技有限公司 Silane waste gas treatment process by combustion washing method

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CN1858091A (en) * 2006-04-25 2006-11-08 扬州大学 Method for treating fluoro rubber by vacuum radio frequency plasma polarization
CN101979429A (en) * 2010-10-14 2011-02-23 中国科学院宁波材料技术与工程研究所 Surface modification method for polytetrafluoroethylene product

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114075348A (en) * 2020-08-14 2022-02-22 南京理工大学 Preparation method of polymerized acrylic monomer on polytetrafluoroethylene microporous membrane
CN117146286A (en) * 2023-10-30 2023-12-01 上海朗蔚环保科技有限公司 Silane waste gas treatment process by combustion washing method

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