CN102688704A - Method for preparing lasting super-hydrophobic modified polypropylene hollow fiber membrane - Google Patents
Method for preparing lasting super-hydrophobic modified polypropylene hollow fiber membrane Download PDFInfo
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- CN102688704A CN102688704A CN2012101815710A CN201210181571A CN102688704A CN 102688704 A CN102688704 A CN 102688704A CN 2012101815710 A CN2012101815710 A CN 2012101815710A CN 201210181571 A CN201210181571 A CN 201210181571A CN 102688704 A CN102688704 A CN 102688704A
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Abstract
The invention relates to a method for implementing super-hydrophobic modification on a polypropylene hollow fiber membrane material, in particular to a method for preparing a lasting super-hydrophobic modified polypropylene hollow fiber membrane. The method comprises the following steps of: respectively dissolving fluorine ester containing unsaturated double bonds, acrylate containing a long alkyl chain, dithiol and a photo-initiator into an acetone solution to prepare a modification solution, soaking a polypropylene membrane treated by normal pressure plasmas into the modification solution, performing ultraviolet irradiation, washing, airing, and thus obtaining a fluorine-containing and long alkyl chain grafted modified polypropylene membrane material. A uniform, lasting and stable super-hydrophobic layer containing fluothane and the long alkyl chain is formed on the surface of the polypropylene membrane material, so that the hydrophobic polymer membrane is endowed with excellent super-hydrophobic property, high water pressure resistance and high air permeability; and the method is simple, good in treatment effect and low in cost, does not produce environment pollution, and is efficient and energy-saving.
Description
Technical field
The present invention relates to a kind of the polypropylene hollow fiber membrane material carried out the method for modifying super hydrophobicity, be specifically related to a kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane.
Background technology
Whole world excessive carbon dioxide discharging is the one of the main reasons that causes the greenhouse effects aggravation.China's emission of carbon-dioxide total amount has surpassed the U.S. at present, ranks first in the world; At this wherein, the carbon dioxide of heat power station discharging accounts for more than 40% of China's CO2 emission total amount.Adopting ethanolamine solutions to capture with the absorption liquid circulation and regeneration technology is to realize one of effective method that collecting carbonic anhydride advances.The main process of this technology is: be absorption liquid with the ethanolamine solutions; Carbon dioxide in the flue gas is carried out absorption and separation; Again with enrichment the ethanolamine solutions of carbon dioxide under the condition of high temperature condition of high vacuum degree, handle, realize the circular regeneration of monoethanolamine absorbent solution.In whole collecting carbonic anhydride flow process, the regeneration of ethanolamine solutions is most important, if can not effectively the carbon dioxide draw in the ethanolamine solutions be come out, this solution just can not recycle, and carbon dioxide also just can not effectively be collected.Can realize the regeneration of monoethanolamine absorption liquid through the high temperature condition of high vacuum degree, but this process energy consumption is big, can bring heavy financial burden to the power station.Even if at present more advanced can be the IGCC technology of hydrogen fuel through the reaction conversion with water with coal fuel, also can bring huge financial burden to heat power station.
Employing is regenerated to the carbon dioxide absorption ethanolamine solutions based on polymer separation film contactor technology and is considered to one of the most promising collecting carbonic anhydride method.With enrichment the ethanolamine solutions of carbon dioxide feed membrane contactor, realize the capture of carbon dioxide and the regeneration of ethanolamine solutions.Adopt polymer separation film with carbon dioxide high efficiency separation from ethanolamine solutions, can effectively reduce the capture cost and the energy savings of carbon dioxide.In journey, because the surface of membrane material inevitably can be wetting by gradually, fenestra is stopped up by ethanolamine solutions and then loses the carbon dioxide eliminating function gradually the polymer separation film contactor to the ethanolamine solutions that is rich in carbon dioxide.Therefore, the key technology of polymer separation film contactor to trap separating carbon dioxide is the preparation of super-hydrophobicity membrane material.Because it is wetted that existing polymeric film material is prone to, service time is short, organic efficiency is low.Therefore, be necessary existing polymeric film material is carried out the ultra water modification in surface, give its excellent ultra-hydrophobicity, high water pressure resistance, persistence difficulty, highly-breathable ability, the operating efficiency of raising diffusion barrier by water infiltration.
Polypropylene is one type of cheap, as to have excellent chemical stability and heat endurance polymeric material; Polypropylene hollow fiber membrane by its preparation has been widely used in fields such as industry, agricultural, medicine, environmental protection, for energy savings, raise the efficiency, environment purification etc. has been made significant contribution.Though the polypropylene hollow fiber membrane surface has certain hydrophobic performance, after the aqueous solution contacted for a long time, the surface of polypropylene screen material still inevitably can be wetting by gradually, and fenestra is stopped up by solution.Adopt some modifier that modification is carried out on the polypropylene hollow fiber membrane surface with excellent hydrophobic performance; Utilize and introduce super hydrophobic functional group raising polypropylene screen hydrophobic properties of the surface; Be expected to polypropylene hollow fiber membrane is applied to embrane method contactor collecting carbonic anhydride, further expand the application of polypropylene screen material.
Summary of the invention
The present invention mainly be overcome polypropylene screen be used for membrane contactor to the ethanolamine solutions that is rich in carbon dioxide after journey; Because the surface of membrane material inevitably can be wetting by gradually; Fenestra is stopped up by ethanolamine solutions and then loses this technological deficiency of carbon dioxide eliminating function gradually, provides a kind of polypropylene hollow fiber membrane is carried out method for modifying super hydrophobicity.
The present invention realizes through following technical scheme:
A kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane may further comprise the steps:
Acrylic acid ester, two mercaptan and the light trigger that (1), will contain the fluorine ester of unsaturated double-bond and contain long alkyl chain are dissolved in the ethanolic solution preparation modified solution;
(2), the polypropylene screen material is placed between two sparking electrodes of dielectric barrier discharge, feed inert gas, carry out the atmospheric dielectric barrier discharge plasma and handle;
(3), the polypropylene screen material after the said processing of step (2) is immersed in the said modified solution of step (1); Carried out ultraviolet light irradiation simultaneously 1 ~ 40 minute; Utilize washed with de-ionized water also at room temperature to dry at last, promptly make the fluorine ester and contain the acrylic acid ester surface grafting polymerization of long alkyl chain and the modifying super hydrophobicity polypropylene screen material of surface-crosslinked modification.
The fluorine ester that contains unsaturated double-bond in the above-mentioned steps (1) can be acrylic acid (N-methyl perfluor sulfonyl amido) ethyl ester C
nF
2n+1SO
2N (CH
3) CH
2CH
2OCOCH=CH
2, wherein, n=6,8,10 and 12; Perfluor alkyl ethide acrylic acid ester C
mF
2m+1CH
2CH
2OCOCH=CH
2, wherein, m=6,8,10 and 12.
The acrylic acid ester that contains long alkyl chain in the above-mentioned steps (1) can be dodecyl acrylic acid ester, myristyl acrylic acid ester, cetyl acrylic acid ester or octadecyl acrylic acid ester.
Two mercaptan in the above-mentioned steps (1) are dithioglycol, 1,4-succinimide mercaptans or 1,6-ethanthiol.
Light trigger in the above-mentioned steps (1) is diphenyl (2,4, the 6-trimethylbenzoyl) phosphine oxide, styrax dimethyl ether, benzophenone, thioxanthones, camphorquinone.
The mass percent concentration that contains the fluorine ester of unsaturated double-bond, the acrylic acid ester that contains long alkyl chain, two mercaptan and light trigger in the modified solution in the above-mentioned steps (1) is respectively 0.1 ~ 10%, 0.1 ~ 10%, 0.05 ~ 2% and 0.001 ~ 0.1%.
Inert gas in the above-mentioned steps (2) is helium or argon gas.
Atmospheric dielectric barrier discharge plasma treatment conditions in the above-mentioned steps (2) are: the distance between two sparking electrodes is 1.5～3 centimetres, feeds inert gas, 0.5～10 liter/minute of gas flow during discharge; Discharge frequency is 10 KHzs, and discharge power is 50～150 watts, and the processing time is 5～30 seconds.
The present invention has following advantage:
The fluorine ester that utilization of the present invention contains unsaturated double-bond carries out self assembly with the acrylic acid ester molecular energy that contains long alkyl chain on the hydrophobic polymer surface; And combine mercapto-alkene click-reaction will contain double-stranded fluorine ester of insatiable hunger and the acrylic acid ester surface grafting polymerization that contains long alkyl chain and surface-crosslinked; And then form evenly at the polypropylene screen material surface, the fluothane of lasting stability and contain the super-hydrophobic layer of long alkyl chain, thereby excellent ultra-hydrophobicity, high water pressure resistance and the highly-breathable ability of hydrophobic property polymer film.Technology of the present invention is simple, treatment effect good, cost is low, non-environmental-pollution, energy-efficient.
The specific embodiment
Reach technological means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with preferred embodiment, to its specific embodiment, structure, characteristic and the effect thereof that proposes according to the present invention, specify as after.
A kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane may further comprise the steps:
Acrylic acid ester, two mercaptan and the light trigger that (1), will contain the fluorine ester of unsaturated double-bond and contain long alkyl chain are dissolved in the ethanolic solution preparation modified solution;
(2), the polypropylene screen material is placed between two sparking electrodes of dielectric barrier discharge, feed inert gas, carry out the atmospheric dielectric barrier discharge plasma and handle;
(3), the polypropylene screen material after the said processing of step (2) is immersed in the said modified solution of step (1); Carried out ultraviolet light irradiation simultaneously 1 ~ 40 minute; Utilize washed with de-ionized water also at room temperature to dry at last, promptly make the fluorine ester and contain the acrylic acid ester surface grafting polymerization of long alkyl chain and the modifying super hydrophobicity polypropylene screen material of surface-crosslinked modification.
The fluorine ester that contains unsaturated double-bond in the above-mentioned steps (1) can be acrylic acid (N-methyl perfluor sulfonyl amido) ethyl ester CnF2n+1SO2N (CH3) CH2CH2OCOCH=CH2, wherein, and n=6,8,10 and 12; Perfluor alkyl ethide acrylic acid ester CmF2m+1CH2CH2OCOCH=CH2, wherein, m=6,8,10 and 12.
The acrylic acid ester that contains long alkyl chain in the above-mentioned steps (1) can be dodecyl acrylic acid ester, myristyl acrylic acid ester, cetyl acrylic acid ester or octadecyl acrylic acid ester.
Two mercaptan in the above-mentioned steps (1) are dithioglycol, 1,4-succinimide mercaptans or 1,6-ethanthiol.
Light trigger in the above-mentioned steps (1) is diphenyl (2,4, the 6-trimethylbenzoyl) phosphine oxide, styrax dimethyl ether, benzophenone, thioxanthones, camphorquinone.
The mass percent concentration that contains the fluorine ester of unsaturated double-bond, the acrylic acid ester that contains long alkyl chain, two mercaptan and light trigger in the modified solution in the above-mentioned steps (1) is respectively 0.1 ~ 10%, 0.1 ~ 10%, 0.05 ~ 2% and 0.001 ~ 0.1%.
Inert gas in the above-mentioned steps (2) is helium or argon gas.
Atmospheric dielectric barrier discharge plasma treatment conditions in the above-mentioned steps (2) are: the distance between two sparking electrodes is 1.5～3 centimetres, feeds inert gas, 0.5～10 liter/minute of gas flow during discharge; Discharge frequency is 10 KHzs, and discharge power is 50～150 watts, and the processing time is 5～30 seconds.
Embodiment 1:
With (N-methyl perfluoro hexyl sulfoamido) ethyl ester (C
6F
13SO
2N (CH
3) CH
2CH
2OCOCH=CH
2) and dodecyl acrylic acid ester, two mercaptan and light trigger mix by 0.1%, 0.1%, 0.05 and 0.001% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.1 ~ 0.9mm, and the film surface contact angle is 108.4 ± 1.3 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 2 centimetres, feeds helium atmosphere, 1 liter/minute of gas flow during discharge; Discharge frequency is 10 KHzs, and discharge power is 80 watts, and the processing time is 10 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified agent solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 2:
With (N-methyl perfluorinated octyl sulfuryl amine base) ethyl ester (C
8F
17SO
2N (CH
3) CH
2CH
2OCOCH=CH
2) and myristyl acrylic acid ester, two mercaptan and light trigger mix by 1%, 1%, 0.1% and 0.005% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.1 ~ 0.9mm, and the film surface contact angle is 108.4 ± 1.3 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 1.5 centimetres, feeds helium atmosphere, 0.5 liter/minute of gas flow during discharge; Discharge frequency is 10 KHzs, and discharge power is 50 watts, and the processing time is 5 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 3:
With (N-methyl perfluor decyl sulfoamido) ethyl ester (C
10F
21SO
2N (CH
3) CH
2CH
2OCOCH=CH
2) and cetyl acrylic acid ester, two mercaptan and light trigger mix by 2%, 2%, 0.3% and 0.01% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.1 ~ 0.9mm, and the film surface contact angle is 108.4 ± 1.3 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 3 centimetres, feeds helium atmosphere, 4 liters/minute of gas flows during discharge; Discharge frequency is 10 KHzs, and discharge power is 100 watts, and the processing time is 20 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 4:
With (N-methyl perfluor dodecyl sulfoamido) ethyl ester (C
12F
21SO
2N (CH
3) CH
2CH
2OCOCH=CH
2) and octadecyl acrylic acid ester, two mercaptan and light trigger mix by 5%, 5%, 1% and 0.05% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.1 ~ 0.9mm, and the film surface contact angle is 108.4 ± 1.3 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 3 centimetres, feeds helium atmosphere, 8 liters/minute of gas flows during discharge; Discharge frequency is 10 KHzs, and discharge power is 120 watts, and the processing time is 30 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 5:
With perflexane base ethyl propylene acid esters (C
6F
13CH
2CH
2OCOCH=CH
2) and octadecyl acrylic acid ester, two mercaptan and light trigger mix by 1%, 5%, 1.5% and 0.05% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.1 ~ 0.9mm, and the film surface contact angle is 108.4 ± 1.3 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 2 centimetres, feeds helium atmosphere, 10 liters/minute of gas flows during discharge; Discharge frequency is 10 KHzs, and discharge power is 150 watts, and the processing time is 30 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 6:
With PFO base ethyl propylene acid esters (C
8F
17CH
2CH
2OCOCH=CH
2) and cetyl acrylic acid ester, two mercaptan and light trigger mix by 4%, 1%, 2% and 0.1% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.02 ~ 0.5mm, and the film surface contact angle is 111.6 ± 2.3 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 3 centimetres, feeds helium atmosphere, 5 liters/minute of gas flows during discharge; Discharge frequency is 10 KHzs, and discharge power is 100 watts, and the processing time is 20 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 7:
With perfluoro decane base ethyl propylene acid esters (C
10F
21CH
2CH
2OCOCH=CH
2) and myristyl acrylic acid ester, two mercaptan and light trigger mix by 8%, 2%, 0.05% and 0.1% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.1 ~ 0.5mm, and the film surface contact angle is 108.5 ± 1.1 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 1.5 centimetres, feeds helium atmosphere, 5 liters/minute of gas flows during discharge; Discharge frequency is 10 KHzs, and discharge power is 50 watts, and the processing time is 10 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 8:
With perfluor dodecyl ethyl propylene acid esters (C
10F
21CH
2CH
2OCOCH=CH
2) and dodecyl acrylic acid ester, two mercaptan and light trigger mix by 2%, 10%, 1% and 0.1% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.02 ~ 0.5mm, and the film surface contact angle is 113.4 ± 3.4 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 3 centimetres, feeds helium atmosphere, 1 liter/minute of gas flow during discharge; Discharge frequency is 10 KHzs, and discharge power is 100 watts, and the processing time is 5 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 9:
With PFO base ethyl propylene acid esters (C
8F
17CH
2CH
2OCOCH=CH
2) and octadecyl acrylic acid ester, two mercaptan and light trigger mix by 5%, 8%, 2% and 0.1% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.01 ~ 0.3mm, and the film surface contact angle is 109.2 ± 1.6 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 3 centimetres, feeds helium atmosphere, 10 liters/minute of gas flows during discharge; Discharge frequency is 10 KHzs, and discharge power is 150 watts, and the processing time is 20 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Embodiment 10:
With perfluoro decane base ethyl propylene acid esters (C
8F
17CH
2CH
2OCOCH=CH
2) and octadecyl acrylic acid ester, two mercaptan and light trigger mix by 10%, 2%, 1.5% and 0.05% concentration ratio and be dissolved in the ethanolic solution preparation hydrophobically modified agent solution.(membrane aperture is 0.01 ~ 0.8mm, and the film surface contact angle is 114.8 ± 4.1 with polypropylene screen
o) be placed in the atmospheric dielectric barrier discharge plasma equipment, regulating between two sparking electrodes distance is 1.5 centimetres, feeds helium atmosphere, 8 liters/minute of gas flows during discharge; Discharge frequency is 10 KHzs, and discharge power is 80 watts, and the processing time is 10 seconds; To be immersed in through the polypropylene screen of plasma treatment in the hydrophobically modified solution of above-mentioned preparation, carry out ultraviolet lighting simultaneously 40 minutes.Taking-up is dried under the room temperature after deionized water is cleaned, and promptly gets the modifying super hydrophobicity polypropylene separation membrane, and its hydrophilicity sees Table 1.
Table 1: polymer-modified separation membrane surface hydrophily of different hydrophilic and persistence table with test results
| ? | Unmodified membrane surface water contact angle | Clean film surface water contact angle 1 time | Clean film surface water contact angle 2 times | Clean 1 day film surface water contact angle | Clean 7 days film surface water contact angles |
| Embodiment 1 | 108.4±1.3 o | 126.9±1.2 o | 126.3± 2.0 o | 124.0± 1.1 o | 123.5± 0.8 o |
| Embodiment 2 | 108.4±1.3 o | 128.5± 2.4 o | 127.4±3.2 ?o | 127.2± 2.7 o | 126.8± 1.5 o |
| Embodiment 3 | 108.4±1.3 o | 130.2± 3.3 o | 128.5± 1.8 o | 129.3± 1.4 o | 128.6± 1.2 o |
| Embodiment 4 | 108.4±1.3 o | 139.9± 2.0 o | 138.2± 3.7 o | 137.0± 1.6 o | 136.9± 1.2 o |
| Embodiment 5 | 108.4±1.3 o | 131.8± 3.4 o | 130.6± 1.9 o | 129.3± 1.5 o | 129.0± 1.0 o |
| Embodiment 6 | 111.6±2.3 o | 136.4± 2.3 o | 135.1± 2.9 o | 135.3± 1.6 o | 134.9± 2.7 o |
| Embodiment 7 | 108.5±1.1 o | 142.6± 3.1 o | 141.9± 2.5 o | 140.3± 2.2 o | 139.5± 1.2 o |
| Embodiment 8 | 113.4±3.4 o | 138.4± 2.9 o | 138.2± 2.2 o | 137.3± 1.8 o | 136.6± 1.1 o |
| Embodiment 9 | 109.2±1.6 o | 140.4± 3.9 o | 140.2± 2.6 o | 139.1± 1.2 o | 137.5± 1.0 o |
| Embodiment 10 | 114.8±4.1 o | 148.4± 3.5 o | 147.6± 2.9 o | 147.2± 2.6 o | 146.6± 1.3 o |
Adopt sessile drop method (Sessile drop method) to measure the water contact angle on film surface.In room temperature (25 ± 1 ℃, relative humidity 45～50%) with being fixed on behind the film cleaning-drying on the smooth bright and clean slide.The Static Water contact angle generally is to get about 5 μ L water droplets to drop in the film surface, photographs the drop curved surface with digital camera immediately, then through the computer The Fitting Calculation, draws the Static Water contact angle of sample.Each sample parallel testing 10 times is obtained mean value, and the result is as shown in table 1.Can find out; Polymer film surface water contact angle through hydrophilic modifying all significantly reduces; And keep stable through the long-term modifying polymer film surface water contact angle that cleans, and then confirmed hydrophily that " a kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane " disclosed by the invention can hydrophobic property polymer separation film lasting stability and biocompatibility.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Though the present invention discloses as above with preferred embodiment; Yet be not in order to limiting the present invention, anyly be familiar with the professional and technical personnel, in not breaking away from technical scheme scope of the present invention; When the technology contents of above-mentioned announcement capable of using is made a little change or is modified to the equivalent embodiment of equivalent variations; In every case be the content that does not break away from technical scheme of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (8)
1. preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane is characterized in that may further comprise the steps:
Acrylic acid ester, two mercaptan and the light trigger that (1), will contain the fluorine ester of unsaturated double-bond and contain long alkyl chain are dissolved in the ethanolic solution preparation modified solution;
(2), the polypropylene screen material is placed between two sparking electrodes of dielectric barrier discharge, feed inert gas, carry out the atmospheric dielectric barrier discharge plasma and handle;
(3), the polypropylene screen material after the said processing of step (2) is immersed in the said modified solution of step (1); Carried out ultraviolet light irradiation simultaneously 1 ~ 40 minute; Utilize washed with de-ionized water also at room temperature to dry at last, promptly make the fluorine ester and contain the acrylic acid ester surface grafting polymerization of long alkyl chain and the modifying super hydrophobicity polypropylene screen material of surface-crosslinked modification.
2. a kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane according to claim 1 is characterized in that the fluorine ester that contains unsaturated double-bond in the said step (1) can be acrylic acid (N-methyl perfluor sulfonyl amido) ethyl ester C
nF
2n+1SO
2N (CH
3) CH
2CH
2OCOCH=CH
2, wherein, n=6,8,10 and 12; Perfluor alkyl ethide acrylic acid ester C
mF
2m+1CH
2CH
2OCOCH=CH
2, wherein, m=6,8,10 and 12.
3. a kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane according to claim 1 is characterized in that the acrylic acid ester that contains long alkyl chain in the said step (1) can be dodecyl acrylic acid ester, myristyl acrylic acid ester, cetyl acrylic acid ester or octadecyl acrylic acid ester.
4. a kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane according to claim 1 is characterized in that two mercaptan in the said step (1) are dithioglycol, 1,4-succinimide mercaptans or 1,6-ethanthiol.
5. a kind of preparation method according to claim 1 with lasting modifying super hydrophobicity polypropylene hollow fiber membrane; It is characterized in that the light trigger in the said step (1) is a diphenyl (2; 4,6-trimethylbenzoyl) phosphine oxide, styrax dimethyl ether, benzophenone, thioxanthones, camphorquinone.
6. a kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane according to claim 1 is characterized in that containing in the modified solution in the said step (1) that the mass percent concentration of the fluorine ester of unsaturated double-bond, the acrylic acid ester that contains long alkyl chain, two mercaptan and light trigger is respectively 0.1 ~ 10%, 0.1 ~ 10%, 0.05 ~ 2% and 0.001 ~ 0.1%.
7. a kind of preparation method with lasting modifying super hydrophobicity polypropylene hollow fiber membrane according to claim 1 is characterized in that the inert gas in the said step (2) is helium or argon gas.
8. a kind of preparation method according to claim 1 with lasting modifying super hydrophobicity polypropylene hollow fiber membrane; It is characterized in that the atmospheric dielectric barrier discharge plasma treatment conditions in the said step (2) are: the distance between two sparking electrodes is 1.5～3 centimetres; Feed inert gas, 0.5～10 liter/minute of gas flow during discharge; Discharge frequency is 10 KHzs, and discharge power is 50～150 watts, and the processing time is 5～30 seconds.
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| CN105597562A (en) * | 2015-12-22 | 2016-05-25 | 贵州省材料产业技术研究院 | Method for performing modification on polymer separation film through ultrasonic in-situ polymerization |
| CN106175018A (en) * | 2016-07-08 | 2016-12-07 | 华南理工大学 | A kind of degradable disponsable hair care towel and preparation method thereof |
| CN106902643A (en) * | 2017-03-30 | 2017-06-30 | 哈尔滨工业大学 | The preparation method and applications of strong-hydrophobicity polypropylene hollow fiber membrane |
| CN109137466A (en) * | 2018-08-17 | 2019-01-04 | 绩溪袁稻农业产业科技有限公司 | Ultraviolet compounding fusion-jetting polypropylene oil absorption non-woven fabrics of one kind and preparation method thereof |
| CN112029325A (en) * | 2020-09-01 | 2020-12-04 | 淮阴工学院 | Preparation method of polyacrylate super-hydrophobic coating |
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| CN106175018A (en) * | 2016-07-08 | 2016-12-07 | 华南理工大学 | A kind of degradable disponsable hair care towel and preparation method thereof |
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| CN112608412A (en) * | 2020-11-06 | 2021-04-06 | 临海伟星新型建材有限公司 | Preparation method of fluorine-containing grafted polyolefin material |
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| CN114262485A (en) * | 2022-03-03 | 2022-04-01 | 上海科进生物技术有限公司 | Modified high polymer material and preparation method and application thereof |
| CN114262485B (en) * | 2022-03-03 | 2022-05-24 | 上海科进生物技术有限公司 | Modified high polymer material and preparation method and application thereof |
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| CN115074989A (en) * | 2022-08-01 | 2022-09-20 | 武汉纺织大学 | Super-hydrophobic Lyocell fabric and preparation method thereof |
| CN115074989B (en) * | 2022-08-01 | 2023-11-24 | 武汉纺织大学 | Super-hydrophobic lyocell fabric and preparation method thereof |
| CN116119993A (en) * | 2023-03-14 | 2023-05-16 | 武昌理工学院 | Light compressive building material for assembled building and preparation method thereof |
| CN116119993B (en) * | 2023-03-14 | 2023-09-22 | 武昌理工学院 | Light compressive building material for assembled building and preparation method thereof |
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