CN114534520B - High-temperature-resistant modified filter membrane - Google Patents
High-temperature-resistant modified filter membrane Download PDFInfo
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- CN114534520B CN114534520B CN202210172010.8A CN202210172010A CN114534520B CN 114534520 B CN114534520 B CN 114534520B CN 202210172010 A CN202210172010 A CN 202210172010A CN 114534520 B CN114534520 B CN 114534520B
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- 239000012528 membrane Substances 0.000 title claims abstract description 62
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 69
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 69
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000853 adhesive Substances 0.000 claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 claims abstract description 41
- -1 polypropylene Polymers 0.000 claims abstract description 30
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004743 Polypropylene Substances 0.000 claims abstract description 27
- 229920001155 polypropylene Polymers 0.000 claims abstract description 27
- 239000012965 benzophenone Substances 0.000 claims abstract description 26
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 239000011256 inorganic filler Substances 0.000 claims abstract description 25
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 25
- 239000004014 plasticizer Substances 0.000 claims abstract description 25
- 229920000800 acrylic rubber Polymers 0.000 claims abstract description 19
- XBXHCBLBYQEYTI-UHFFFAOYSA-N piperidin-4-ylmethanol Chemical compound OCC1CCNCC1 XBXHCBLBYQEYTI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims abstract description 9
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 63
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical compound CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000391 magnesium silicate Substances 0.000 claims description 8
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 8
- 235000019792 magnesium silicate Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012990 dithiocarbamate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BSSMSDMDCCVWTE-UHFFFAOYSA-N 4-(benzhydryloxymethyl)piperidine Chemical compound C1CNCCC1COC(C=1C=CC=CC=1)C1=CC=CC=C1 BSSMSDMDCCVWTE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WOSBVBMEPDUCPG-UHFFFAOYSA-N C(CCC)OCCCC.[Li] Chemical compound C(CCC)OCCCC.[Li] WOSBVBMEPDUCPG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a high-temperature resistant modified filter membrane, which comprises a polypropylene base membrane and a modified membrane, wherein the upper surface and the lower surface of the polypropylene base membrane are respectively coated with a layer of modified membrane, the modified membrane comprises the following raw materials of 50-60 parts by weight of polyvinylidene chloride, 5-6 parts by weight of ethylene-alkyl acrylate copolymer, 5-7 parts by weight of benzophenone, 1-3 parts by weight of butyllithium, 2-4 parts by weight of 4-hydroxymethyl piperidine, 0.5-1 part by weight of heat stabilizer, 1-3 parts by weight of dispersing agent, 5-7 parts by weight of adhesive, 0.5-1 part by weight of inorganic filler and 2.5-3 parts by weight of plasticizer, and the heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate. The polyvinylidene chloride has symmetrical performance, has stronger flame retardance, corrosion resistance and biodegradation resistance, and the modified polyvinylidene chloride has improved flexibility, cold resistance and heat resistance by using the ethylene-alkyl acrylate copolymer.
Description
Technical Field
The invention relates to the technical field of filter membrane preparation, in particular to a high-temperature-resistant modified filter membrane.
Background
The filter membrane can separate solutes in the solution, along with continuous progress of technology, the modification of the membrane becomes a common main means for enhancing the performance of the membrane in all aspects, and the main method of modification is a physical and chemical method, and the overall performance is enhanced by introducing other high polymer resins, so that the defects are overcome.
Polyvinylidene chloride has symmetrical performance, strong flame retardance, corrosion resistance and biodegradability resistance, and has wide application in the field of filter membrane preparation, but polyvinylidene chloride has the defect of poor thermal stability, and after membrane preparation is finished, the polyvinylidene chloride needs to be dried and baked, and the polyvinylidene chloride is decomposed in the drying and baking process due to high temperature, so that the tensile strength and thermal stability of the product are reduced, and hydrogen chloride gas can be released, so that the quality of the membrane is influenced, and harm is caused to human bodies and the environment, so that the high-temperature-resistant modified filter membrane and the preparation process thereof are particularly important.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant modified filter membrane and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the high temperature resistant modified filter membrane comprises a polypropylene base membrane and a modified membrane, wherein the upper surface and the lower surface of the polypropylene base membrane are respectively coated with a layer of modified membrane.
Further, the modified film comprises, by weight, 50-60 parts of polyvinylidene chloride, 5-6 parts of ethylene-alkyl acrylate copolymer, 5-7 parts of benzophenone, 1-3 parts of butyllithium, 2-4 parts of 4-hydroxymethylpiperidine, 0.5-1 part of heat stabilizer, 1-3 parts of dispersing agent, 5-7 parts of adhesive, 0.5-1 part of inorganic filler and 2.5-3 parts of plasticizer.
Further, the heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate.
Further, the plasticizer is one or two of dioctyl adipate and citric acid ester.
Further, the adhesive is one or two of ethylene-vinyl acetate copolymer and copolymer of acrylic acid and acrylonitrile.
Further, the inorganic filler is one or more of calcium carbonate, titanium dioxide and magnesium silicate.
Further, the dispersing agent is one or a mixture of a plurality of triethylhexyl phosphoric acid, methyl amyl alcohol and fatty acid polyethylene glycol ester.
A preparation process of a high temperature resistant modified filter membrane comprises the following steps,
(1) Placing polyvinylidene chloride into methanol solution, soaking and washing for three times, taking out, drying, and controlling the temperature to 40-45 ℃ for standby;
(2) Putting the polyvinylidene chloride obtained in the step (1) into diethyl ether, adding benzophenone, immersing the polyvinylidene chloride into the benzophenone completely, carrying out ultraviolet irradiation, and drying for later use;
(3) Putting the polyvinylidene chloride obtained in the step (2) into diethyl ether solution, adding ethylene-alkyl acrylate copolymer, carrying out ultraviolet irradiation, separating, and recovering solvent to obtain a modified polyvinylidene chloride film;
(4) Dissolving the adhesive in an organic solvent, stirring, adding a plasticizer, and stirring uniformly to obtain an adhesive solvent;
(5) Adding 4-hydroxymethyl piperidine into the solvent obtained in the step (3), introducing nitrogen, stirring, adding butyl lithium, stirring, reacting for 5-10min, adding deionized water, stirring, adding a heat stabilizer and an inorganic filler, uniformly stirring, adding a dispersing agent, stirring, adding an adhesive solvent, stirring, placing a modified polyvinylidene chloride film, standing for 1-2h, taking out, covering the upper and lower surfaces of the polypropylene base film, vacuum drying, baking, and obtaining the high-temperature-resistant modified filter film at 90-100 ℃.
Further, in the step (5), the concentration of butyllithium added was 1.5mol/L.
In the step (2) and the step (3), nitrogen is required to be introduced during ultraviolet irradiation, and the irradiation time is 10-15min.
Compared with the prior art, the invention has the following beneficial effects: the polyvinylidene chloride has symmetrical performance, has stronger flame retardance, corrosion resistance and biodegradation resistance, has the defect that the polyvinylidene chloride has poor thermal stability, can be decomposed in the subsequent drying and baking processes, so that the tensile strength and thermal stability of the product are reduced, and hydrogen chloride gas can be released to cause harm to human bodies and the environment.
According to the invention, the polyvinylidene chloride is modified by adopting an ultraviolet irradiation mode, and the diphenyl ketone is used as a photoinitiator to enable the ethylene-alkyl acrylate copolymer to be grafted onto the polyvinylidene chloride, so that the tensile strength and cold resistance and heat resistance of the film are improved, and as the carbonyl bond of the diphenyl ketone is broken in the reaction and hydrogen ions are absorbed, alcohol substances are obtained, mainly diphenyl methanol which can be dissolved in the diethyl ether, and the diphenyl methanol is extremely unstable under the action of high temperature and strong oxidant due to the self property, after the modification is finished, a part of the diphenyl methanol is attached to the surface of the film, so that the tensile strength, flame retardant property and heat stability of the product are reduced, but as the boiling point of the diphenyl methanol is high, the diphenyl methanol can volatilize only at more than 290 ℃, and the polyvinylidene chloride can be decomposed at 120 ℃, so that the conventional high-temperature alcohol and water removal mode is not applicable any more; aiming at the problem, the invention introduces 4-hydroxymethyl piperidine and butyl lithium, and the 4-hydroxymethyl piperidine can absorb the benzhydrol in the presence of the butyl lithium, so that the content of the benzhydrol is reduced, the adhesion of the benzhydrol is avoided, and further, the tensile strength and the thermal stability of the product are ensured.
Meanwhile, the 4-hydroxymethyl piperidine can be used as a degerming agent, 4- ((diphenyl methoxy) methyl) piperidine can be generated in the process of absorbing the benzhydrol, and the product has excellent degerming performance, so that the degerming capability is ensured not to be reduced due to the consumption of the 4-hydroxymethyl piperidine.
Butyl lithium has stronger reducibility, and the product film can be corroded by the excessive concentration, so that the qualification rate is reduced, and the added concentration is required to be controlled to be 1.5mol/L, so that the qualification rate of the film is ensured.
After the preparation is finished, drying and baking are needed, the temperature is 90-100 ℃, and although the temperature is lower, a small part of polyvinylidene chloride is still decomposed to release hydrogen chloride gas, the tensile strength and the thermal stability of a product film are reduced due to the generation of hydrogen chloride, the lithium butyl oxide introduced by the invention can undergo a lithiation reaction to generate a small amount of lithium hydroxide, and the lithium hydroxide can absorb the hydrogen chloride, so that the occurrence of secondary damage to the product film due to the volatilized hydrogen chloride gas is reduced, and the tensile strength and the thermal stability of the product film are further improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The high temperature resistant modified filter membrane comprises a polypropylene base membrane and a modified membrane, wherein the upper surface and the lower surface of the polypropylene base membrane are respectively coated with a layer of modified membrane.
The modified film comprises the following raw materials in parts by weight, namely 50 parts of polyvinylidene chloride, 5 parts of ethylene-alkyl acrylate copolymer, 5 parts of benzophenone, 1 part of butyl lithium, 2 parts of 4-hydroxymethyl piperidine, 0.5 part of heat stabilizer, 1 part of dispersant, 5 parts of adhesive, 0.5 part of inorganic filler and 2.5 parts of plasticizer.
The heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate.
The plasticizer is one or two of dioctyl adipate and citrate.
The adhesive is one or two of ethylene-vinyl acetate copolymer and acrylic acid and acrylonitrile copolymer.
The inorganic filler is one or more of calcium carbonate, titanium dioxide and magnesium silicate.
The dispersing agent is one or a mixture of a plurality of triethylhexyl phosphoric acid, methyl amyl alcohol and fatty acid polyethylene glycol ester.
A preparation process of a high temperature resistant modified filter membrane comprises the following steps,
(1) Placing polyvinylidene chloride into a methanol solution, immersing and washing for three times, taking out, drying, and controlling the temperature to 40 ℃ for standby;
(2) Putting the polyvinylidene chloride obtained in the step (1) into diethyl ether, adding benzophenone, immersing the polyvinylidene chloride in the benzophenone completely, carrying out ultraviolet irradiation, introducing nitrogen for 10min, and drying for later use;
(3) Putting the polyvinylidene chloride obtained in the step (2) into an diethyl ether solution, adding an ethylene-alkyl acrylate copolymer, performing ultraviolet irradiation, introducing nitrogen for 10min, separating, and recovering a solvent to obtain a modified polyvinylidene chloride film;
(4) Dissolving the adhesive in an organic solvent, stirring, adding a plasticizer, and stirring uniformly to obtain an adhesive solvent;
(5) Adding 4-hydroxymethyl piperidine into the solvent obtained in the step (3), introducing nitrogen, stirring, adding 1.5mol/L butyl lithium, stirring for 5min, adding deionized water, stirring, adding a heat stabilizer and an inorganic filler, uniformly stirring, adding a dispersing agent, stirring, adding an adhesive solvent, stirring, putting a modified polyvinylidene chloride film, standing for 1h, taking out, covering the upper and lower surfaces of the polypropylene base film, vacuum drying, baking at 90 ℃ to obtain the high-temperature-resistant modified filter film.
Example 2
The high temperature resistant modified filter membrane comprises a polypropylene base membrane and a modified membrane, wherein the upper surface and the lower surface of the polypropylene base membrane are respectively coated with a layer of modified membrane.
The modified film comprises the following raw materials in parts by weight, namely 55 parts of polyvinylidene chloride, 5 parts of ethylene-alkyl acrylate copolymer, 6 parts of benzophenone, 2 parts of butyl lithium, 3 parts of 4-hydroxymethyl piperidine, 0.7 part of heat stabilizer, 2 parts of dispersing agent, 6 parts of adhesive, 0.7 part of inorganic filler and 2.8 parts of plasticizer.
The heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate.
The plasticizer is one or two of dioctyl adipate and citrate.
The adhesive is one or two of ethylene-vinyl acetate copolymer and acrylic acid and acrylonitrile copolymer.
The inorganic filler is one or more of calcium carbonate, titanium dioxide and magnesium silicate.
The dispersing agent is one or a mixture of a plurality of triethylhexyl phosphoric acid, methyl amyl alcohol and fatty acid polyethylene glycol ester.
A preparation process of a high temperature resistant modified filter membrane comprises the following steps,
(1) Placing polyvinylidene chloride into a methanol solution, immersing and washing for three times, taking out, drying, and controlling the temperature to be 43 ℃ for standby;
(2) Putting the polyvinylidene chloride obtained in the step (1) into diethyl ether, adding benzophenone, immersing the polyvinylidene chloride in the benzophenone completely, carrying out ultraviolet irradiation, introducing nitrogen for 13min, and drying for later use;
(3) Putting the polyvinylidene chloride obtained in the step (2) into an diethyl ether solution, adding an ethylene-alkyl acrylate copolymer, performing ultraviolet irradiation, introducing nitrogen for 13min, separating, and recovering a solvent to obtain a modified polyvinylidene chloride film;
(4) Dissolving the adhesive in an organic solvent, stirring, adding a plasticizer, and stirring uniformly to obtain an adhesive solvent;
(5) Adding 4-hydroxymethyl piperidine into the solvent obtained in the step (3), introducing nitrogen, stirring, adding 1.5mol/L butyl lithium, stirring for 7min, adding deionized water, stirring, adding a heat stabilizer and an inorganic filler, uniformly stirring, adding a dispersing agent, stirring, adding an adhesive solvent, stirring, putting a modified polyvinylidene chloride film, standing for 1.5h, taking out, covering the upper and lower surfaces of a polypropylene base film, vacuum drying, baking at 95 ℃ to obtain the high-temperature-resistant modified filter film.
Example 3
The high temperature resistant modified filter membrane comprises a polypropylene base membrane and a modified membrane, wherein the upper surface and the lower surface of the polypropylene base membrane are respectively coated with a layer of modified membrane.
The modified film comprises the following raw materials in parts by weight, namely 60 parts of polyvinylidene chloride, 6 parts of ethylene-alkyl acrylate copolymer, 7 parts of benzophenone, 3 parts of butyl lithium, 4 parts of 4-hydroxymethyl piperidine, 1 part of heat stabilizer, 3 parts of dispersing agent, 7 parts of adhesive, 1 part of inorganic filler and 3 parts of plasticizer.
The heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate.
The plasticizer is one or two of dioctyl adipate and citrate.
The adhesive is one or two of ethylene-vinyl acetate copolymer and acrylic acid and acrylonitrile copolymer.
The inorganic filler is one or more of calcium carbonate, titanium dioxide and magnesium silicate.
The dispersing agent is one or a mixture of a plurality of triethylhexyl phosphoric acid, methyl amyl alcohol and fatty acid polyethylene glycol ester.
A preparation process of a high temperature resistant modified filter membrane comprises the following steps,
(1) Placing polyvinylidene chloride into a methanol solution, immersing and washing for three times, taking out, drying, and controlling the temperature to be 45 ℃ for standby;
(2) Putting the polyvinylidene chloride obtained in the step (1) into diethyl ether, adding benzophenone, immersing the polyvinylidene chloride in the benzophenone completely, carrying out ultraviolet irradiation, introducing nitrogen for 15min, and drying for later use;
(3) Putting the polyvinylidene chloride obtained in the step (2) into an diethyl ether solution, adding an ethylene-alkyl acrylate copolymer, performing ultraviolet irradiation, introducing nitrogen for 15min, separating, and recovering a solvent to obtain a modified polyvinylidene chloride film;
(4) Dissolving the adhesive in an organic solvent, stirring, adding a plasticizer, and stirring uniformly to obtain an adhesive solvent;
(5) Adding 4-hydroxymethyl piperidine into the solvent obtained in the step (3), introducing nitrogen, stirring, adding 1.5mol/L butyl lithium, stirring for 10min, adding deionized water, stirring, adding a heat stabilizer and an inorganic filler, uniformly stirring, adding a dispersing agent, stirring, adding an adhesive solvent, stirring, putting a modified polyvinylidene chloride film, standing for 2h, taking out, covering the upper and lower surfaces of the polypropylene base film, vacuum drying, baking at 100 ℃ to obtain the high-temperature-resistant modified filter film.
Comparative example 1
The high temperature resistant modified filter membrane comprises a polypropylene base membrane and a modified membrane, wherein the upper surface and the lower surface of the polypropylene base membrane are respectively coated with a layer of modified membrane.
The modified film comprises the following raw materials in parts by weight, namely 60 parts of polyvinylidene chloride, 6 parts of ethylene-alkyl acrylate copolymer, 7 parts of benzophenone, 3 parts of butyl lithium, 4 parts of dithiocarbamic acid ester, 1 part of heat stabilizer, 3 parts of dispersing agent, 7 parts of adhesive, 1 part of inorganic filler and 3 parts of plasticizer.
The heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate.
The plasticizer is one or two of dioctyl adipate and citrate.
The adhesive is one or two of ethylene-vinyl acetate copolymer and acrylic acid and acrylonitrile copolymer.
The inorganic filler is one or more of calcium carbonate, titanium dioxide and magnesium silicate.
The dispersing agent is one or a mixture of a plurality of triethylhexyl phosphoric acid, methyl amyl alcohol and fatty acid polyethylene glycol ester.
A preparation process of a high temperature resistant modified filter membrane comprises the following steps,
(1) Placing polyvinylidene chloride into a methanol solution, immersing and washing for three times, taking out, drying, and controlling the temperature to be 45 ℃ for standby;
(2) Putting the polyvinylidene chloride obtained in the step (1) into diethyl ether, adding benzophenone, immersing the polyvinylidene chloride in the benzophenone completely, carrying out ultraviolet irradiation, introducing nitrogen for 15min, and drying for later use;
(3) Putting the polyvinylidene chloride obtained in the step (2) into an diethyl ether solution, adding an ethylene-alkyl acrylate copolymer, performing ultraviolet irradiation, introducing nitrogen for 15min, separating, and recovering a solvent to obtain a modified polyvinylidene chloride film;
(4) Dissolving the adhesive in an organic solvent, stirring, adding a plasticizer, and stirring uniformly to obtain an adhesive solvent;
(5) Adding dithiocarbamate into the solvent obtained in the step (3), stirring, adding butyl lithium with the concentration of 1.5mol/L, stirring, reacting for 10min, adding deionized water, stirring, adding a heat stabilizer and an inorganic filler, uniformly stirring, adding a dispersing agent, stirring, adding an adhesive solvent, stirring, putting a modified polyvinylidene chloride film, standing for 2h, taking out, covering the upper and lower surfaces of the polypropylene base film, drying in vacuum, and baking at the temperature of 100 ℃ to obtain the high-temperature-resistant modified filter film.
Comparative example 2
The high temperature resistant modified filter membrane comprises a polypropylene base membrane and a modified membrane, wherein the upper surface and the lower surface of the polypropylene base membrane are respectively coated with a layer of modified membrane.
The modified film comprises the following raw materials in parts by weight, namely 60 parts of polyvinylidene chloride, 6 parts of ethylene-alkyl acrylate copolymer, 7 parts of benzophenone, 4 parts of 4-hydroxymethyl piperidine, 1 part of heat stabilizer, 3 parts of dispersing agent, 7 parts of adhesive, 1 part of inorganic filler and 3 parts of plasticizer.
The heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate.
The plasticizer is one or two of dioctyl adipate and citrate.
The adhesive is one or two of ethylene-vinyl acetate copolymer and acrylic acid and acrylonitrile copolymer.
The inorganic filler is one or more of calcium carbonate, titanium dioxide and magnesium silicate.
The dispersing agent is one or a mixture of a plurality of triethylhexyl phosphoric acid, methyl amyl alcohol and fatty acid polyethylene glycol ester.
A preparation process of a high temperature resistant modified filter membrane comprises the following steps,
(1) Placing polyvinylidene chloride into a methanol solution, immersing and washing for three times, taking out, drying, and controlling the temperature to be 45 ℃ for standby;
(2) Putting the polyvinylidene chloride obtained in the step (1) into diethyl ether, adding benzophenone, immersing the polyvinylidene chloride in the benzophenone completely, carrying out ultraviolet irradiation, introducing nitrogen for 15min, and drying for later use;
(3) Putting the polyvinylidene chloride obtained in the step (2) into an diethyl ether solution, adding an ethylene-alkyl acrylate copolymer, performing ultraviolet irradiation, introducing nitrogen for 15min, separating, and recovering a solvent to obtain a modified polyvinylidene chloride film;
(4) Dissolving the adhesive in an organic solvent, stirring, adding a plasticizer, and stirring uniformly to obtain an adhesive solvent;
(5) Adding 4-hydroxymethyl piperidine into the solvent obtained in the step (3), stirring, reacting for 10min, adding deionized water, stirring, adding a heat stabilizer and an inorganic filler, uniformly stirring, adding a dispersing agent, stirring, adding an adhesive solvent, stirring, placing a modified polyvinylidene chloride film, standing for 2h, taking out, covering the upper and lower surfaces of a polypropylene base film, vacuum drying, baking at 100 ℃, and obtaining the high-temperature-resistant modified filter film.
Comparative example 3
The high temperature resistant modified filter membrane comprises a polypropylene base membrane and a modified membrane, wherein the upper surface and the lower surface of the polypropylene base membrane are respectively coated with a layer of modified membrane.
The modified film comprises the following raw materials in parts by weight, namely 60 parts of polyvinylidene chloride, 6 parts of ethylene-alkyl acrylate copolymer, 7 parts of benzophenone, 3 parts of phenylmagnesium bromide, 4 parts of 4-hydroxymethylpiperidine, 1 part of heat stabilizer, 3 parts of dispersing agent, 7 parts of adhesive, 1 part of inorganic filler and 3 parts of plasticizer.
The heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate.
The plasticizer is one or two of dioctyl adipate and citrate.
The adhesive is one or two of ethylene-vinyl acetate copolymer and acrylic acid and acrylonitrile copolymer.
The inorganic filler is one or more of calcium carbonate, titanium dioxide and magnesium silicate.
The dispersing agent is one or a mixture of a plurality of triethylhexyl phosphoric acid, methyl amyl alcohol and fatty acid polyethylene glycol ester.
A preparation process of a high temperature resistant modified filter membrane comprises the following steps,
(1) Placing polyvinylidene chloride into a methanol solution, immersing and washing for three times, taking out, drying, and controlling the temperature to be 45 ℃ for standby;
(2) Putting the polyvinylidene chloride obtained in the step (1) into diethyl ether, adding benzophenone, immersing the polyvinylidene chloride in the benzophenone completely, carrying out ultraviolet irradiation, introducing nitrogen for 15min, and drying for later use;
(3) Putting the polyvinylidene chloride obtained in the step (2) into an diethyl ether solution, adding an ethylene-alkyl acrylate copolymer, performing ultraviolet irradiation, introducing nitrogen for 15min, separating, and recovering a solvent to obtain a modified polyvinylidene chloride film;
(4) Dissolving the adhesive in an organic solvent, stirring, adding a plasticizer, and stirring uniformly to obtain an adhesive solvent;
(5) Adding 4-hydroxymethyl piperidine into the solvent obtained in the step (3), introducing nitrogen, stirring, adding phenylmagnesium bromide, stirring, reacting for 10min, adding deionized water, stirring, adding a heat stabilizer and an inorganic filler, uniformly stirring, adding a dispersing agent, stirring, adding an adhesive solvent, stirring, placing a modified polyvinylidene chloride film, standing for 2h, taking out, covering the upper and lower surfaces of the polypropylene base film, vacuum drying, baking, and obtaining the high-temperature-resistant modified filter film at 100 ℃.
Experiment
In the case of example 3, comparative examples 1, 2 and 3 were prepared, in which dithiocarbamate was used as the degerming agent in comparative example 1, butyllithium was not added in comparative example 2, and phenylmagnesium bromide was used in comparative example 3, and a control experiment was performed.
3 parts of each of example 1, example 2, example 3, comparative example 1, comparative example 2 and comparative example 3 were subjected to a tensile strength test by GB/T1040-2006, a heat shrinkage test by a GB/T13542.2-2009 method and a flame retardant property test by a GB2408-80, and the results are as follows,
list one
At the same thickness, the tensile strength, heat shrinkage and flame retardant property of comparative example 1 were lower than those of examples 1, 2 and 3, because dithiocarbamate was used as the degerming agent in comparative example 1, so that excessive benzophenone remained on the solvent and film surface, resulting in a decrease in tensile strength, heat shrinkage and flame retardant property.
At the same thickness, the tensile strength, heat shrinkage and flame retardance of comparative examples 2 and 3 are lower than those of examples 1, 2 and 3, because butyl lithium is not added in comparative example 2, but phenyl magnesium bromide is used in comparative example 3, butyl lithium is used as a catalyst on one hand, and hydrogen chloride is absorbed on the other hand, so that the tensile strength, heat shrinkage and flame retardance of the product are ensured, and butyl lithium is not contained in comparative example 2, so that the performances of the product in various aspects are reduced, and the product film is reduced in tensile strength, heat shrinkage and flame retardance by replacing the phenyl magnesium bromide in comparative example 3, and can only be used as a catalyst and cannot absorb hydrogen chloride.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. The utility model provides a high temperature resistant modified filter membrane which characterized in that: the polypropylene base film comprises a polypropylene base film and a modified film, wherein the upper surface and the lower surface of the polypropylene base film are respectively coated with a layer of modified film;
the modified film comprises the following raw materials in parts by weight, namely 50 parts of polyvinylidene chloride, 5 parts of ethylene-alkyl acrylate copolymer, 5 parts of benzophenone, 1 part of butyl lithium, 2 parts of 4-hydroxymethyl piperidine, 0.5 part of heat stabilizer, 1 part of dispersant, 5 parts of adhesive, 0.5 part of inorganic filler and 2.5 parts of plasticizer;
the heat stabilizer is one or more of barium stearate, lithium stearate and epoxy stearate; the plasticizer is one or two of dioctyl adipate and citrate; the adhesive is one or two of ethylene-vinyl acetate copolymer, acrylic acid and acrylonitrile copolymer; the inorganic filler is one or more of calcium carbonate, titanium dioxide and magnesium silicate; the dispersing agent is one or a mixture of a plurality of triethylhexyl phosphoric acid, methyl amyl alcohol and fatty acid polyethylene glycol ester;
the preparation process of the filter membrane comprises the following steps:
(1) Placing polyvinylidene chloride into a methanol solution, immersing and washing for three times, taking out, drying, and controlling the temperature to 40 ℃ for standby;
(2) Putting the polyvinylidene chloride obtained in the step (1) into diethyl ether, adding benzophenone, immersing the polyvinylidene chloride in the benzophenone completely, carrying out ultraviolet irradiation, introducing nitrogen for 10min, and drying for later use;
(3) Putting the polyvinylidene chloride obtained in the step (2) into an diethyl ether solution, adding an ethylene-alkyl acrylate copolymer, performing ultraviolet irradiation, introducing nitrogen for 10min, separating, and recovering a solvent to obtain a modified polyvinylidene chloride film;
(4) Dissolving the adhesive in an organic solvent, stirring, adding a plasticizer, and stirring uniformly to obtain an adhesive solvent;
(5) Adding 4-hydroxymethyl piperidine into the solvent obtained in the step (3), introducing nitrogen, stirring, adding 1.5mol/L butyl lithium, stirring for 5min, adding deionized water, stirring, adding a heat stabilizer and an inorganic filler, uniformly stirring, adding a dispersing agent, stirring, adding an adhesive solvent, stirring, putting a modified polyvinylidene chloride film, standing for 1h, taking out, covering the upper and lower surfaces of the polypropylene base film, vacuum drying, baking at 90 ℃ to obtain the high-temperature-resistant modified filter film.
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