CN115746636B - Friction-resistant coating dispersion liquid for fluorine-containing ion exchange membrane and coating - Google Patents
Friction-resistant coating dispersion liquid for fluorine-containing ion exchange membrane and coating Download PDFInfo
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- CN115746636B CN115746636B CN202211542690.4A CN202211542690A CN115746636B CN 115746636 B CN115746636 B CN 115746636B CN 202211542690 A CN202211542690 A CN 202211542690A CN 115746636 B CN115746636 B CN 115746636B
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- 238000000576 coating method Methods 0.000 title claims abstract description 140
- 239000011248 coating agent Substances 0.000 title claims abstract description 136
- 239000006185 dispersion Substances 0.000 title claims abstract description 72
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 65
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 48
- 239000011737 fluorine Substances 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims abstract description 41
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000000654 additive Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000010954 inorganic particle Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 11
- 238000005299 abrasion Methods 0.000 claims description 9
- 239000004811 fluoropolymer Substances 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 7
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical group CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 6
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 claims description 6
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004815 dispersion polymer Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003456 ion exchange resin Substances 0.000 description 12
- 229920003303 ion-exchange polymer Polymers 0.000 description 12
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- -1 dodecyl ester Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- SKSIDEOZXDVBGN-UHFFFAOYSA-N fluoro dihydrogen phosphate Chemical compound OP(O)(=O)OF SKSIDEOZXDVBGN-UHFFFAOYSA-N 0.000 description 1
- CKFGINPQOCXMAZ-UHFFFAOYSA-N formaldehyde hydrate Natural products OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of ion exchange membranes, and particularly relates to an antifriction coating dispersion liquid and a coating for a fluorine-containing ion exchange membrane. The friction-resistant coating dispersion for the fluorine-containing ion exchange membrane comprises inorganic particles, at least one fluorine-containing polymer and further comprises an additive diethylene glycol and/or diethylene glycol derivatives. The coating prepared from the antifriction coating dispersion liquid has excellent antifriction performance, can meet the requirements of the coating on antifriction performance in the production, packaging, transportation and use processes of the ion exchange membrane, and improves the comprehensive use performance of the ion exchange membrane.
Description
Technical Field
The invention belongs to the technical field of ion exchange membranes, and particularly relates to an antifriction coating dispersion liquid and a coating for a fluorine-containing ion exchange membrane.
Background
Ion exchange membranes have been widely used in electrolytic oxidation and reduction operations due to their excellent permselectivity. The use of perfluorinated ion exchange membranes in the brine electrolysis industry has led to a revolutionary change in the chlor-alkali industry. In recent years, ion exchange membranes having more stable performance have been demanded for improving production efficiency and reducing energy consumption, and it has been desired that ion exchange membranes be capable of performing electrolysis under conditions of high current density, low cell voltage and high alkali concentration.
However, in the current production, packaging, transportation and practical application processes of the ion exchange membrane, the following conditions occur: the coating formed by coating the surface of the ion exchange membrane is very easy to fall off when being rubbed due to low firmness between the ion exchange membrane and the ion exchange membrane matrix, so that the uneven coating condition appears on the surface of the ion exchange membrane, and the coating is classified as defective products in the production and packaging processes, thereby reducing the qualification rate of products; more serious conditions are that if the coating is severely dropped off in a large area, the voltage of the electrolytic tank is seriously increased during electrolytic production, and the safe and efficient operation of the electrolytic tank is affected.
The occurrence of the above problems severely restricts the overall efficiency of the production of the ion exchange membrane. Thus, there is a need to address the issue of robustness of ion exchange membrane coatings.
Disclosure of Invention
The invention aims to provide an antifriction coating dispersion liquid for a fluorine-containing ion exchange membrane and a coating thereof, aiming at the problem that the firmness between the conventional coating for the fluorine-containing ion exchange membrane and an ion exchange membrane substrate is low. The coating prepared from the antifriction coating dispersion liquid has excellent antifriction performance, can meet the requirements of the coating on antifriction performance in the production, packaging, transportation and use processes of the ion exchange membrane, and improves the comprehensive use performance of the ion exchange membrane.
The technical scheme of the invention is as follows: an antifriction coating dispersion for fluorine-containing ion exchange membranes comprises inorganic particles, at least one fluorine-containing polymer and further comprises the additives diethylene glycol and/or diethylene glycol derivatives. The addition of the additive diethylene glycol and/or diethylene glycol derivative in the ion exchange membrane coating dispersion improves the binding capacity between the fluoropolymer in the coating and the ion exchange membrane matrix resin, thereby improving the coating firmness of the ion exchange membrane.
Diethylene glycol or diethylene glycol derivatives contain more hydroxyl groups, and can form hydrogen bonds with F with smaller radius and larger electronegativity in fluorine-containing polymers (such as fluorine-containing polymers in coating solution and fluorine-containing polymers used for ion exchange membrane matrix), thereby increasing acting force among molecules and improving coating firmness. Meanwhile, the boiling point of the diethylene glycol or the diethylene glycol derivative is very high, for example, the boiling point of the diethylene glycol can reach 245 ℃, and even when high-temperature curing is needed in the curing process of the coating, the diethylene glycol or the diethylene glycol derivative cannot volatilize due to the high temperature of curing based on the characteristic, can be well reserved in the coating, and can still increase acting force among molecules, so that the purpose of improving the firmness of the coating is achieved.
The addition of inorganic particles can improve the roughness of the coating to a certain extent, and a peak/valley structure is constructed on the surface of the ion exchange membrane. Because the current ion exchange membrane adopts the main zero-pole distance or narrow-pole distance structure of the electrolytic cell structure, when the surface of the ion membrane with certain roughness is close to the pole net of the electrolytic cell electrode, the construction of the mountain/valley structure is beneficial to the desorption of bubbles in the electrolytic process, the adhesion of the bubbles on the surface of the ion membrane is avoided, the effective electrolytic area is reduced, the ion conduction resistance is increased, and the electricity consumption is increased. Meanwhile, the surfaces of the inorganic particles are provided with a large number of hydroxyl groups, so that the hydrophilicity of the coating can be improved, and the gas-repellent capacity is improved.
Further, the diethylene glycol derivative in the dispersion of the friction-resistant coating for the fluorine-containing ion exchange membrane is diethylene glycol C 4 H 10 O 3 And C x H y (OH) z Wherein x is 4 or less, y=2x+2-z, z is 3 or less;
preferably, the diethylene glycol derivative is diethylene glycol diethyl ether C 6 H 14 O 3 Diethylene glycol propyl ether C 7 H 16 O 3 Or diethylene glycol butyl ether C 8 H 18 O 3 。
Further, the total addition amount of the diethylene glycol and/or diethylene glycol derivatives as additives in the abrasion-resistant coating dispersion for the fluorine-containing ion exchange membrane is 0.5-5% of the mass of the coating dispersion. The mass fraction of the fluorine-containing polymer in the dispersion liquid is 60% -80%; the mass fraction of the inorganic particles is 15% -35%.
Further, the inorganic particles in the fluorine-containing ion exchange membrane friction-resistant coating dispersion have a particle diameter of 20nm to 10 [ mu ] m.
When the particle size of the inorganic particles is smaller than 20nm, the surface of the ion exchange membrane is constructed with relatively small shape roughness, which is not beneficial to desorption of surface bubbles and increases the electricity consumption; when the particle size is larger than 10 mu m, the coating solution is unfavorable for coating inorganic particles, and meanwhile, the formed coating has overlarge shape roughness, so that the firmness of the coating is unfavorable for improvement.
Further, the inorganic substance is at least one selected from oxides, hydroxides and nitrides of elements of groups IV-A, IV-B, V-B and III-B.
Preferably, the inorganic substance is at least one of zirconia, silica, zirconia and yttria.
Further, the fluoropolymer in the fluorine-containing ion exchange membrane friction-resistant coating dispersion contains sulfonic acid groups, carboxylic acid groups or phosphoric acid groups.
Further, the fluoropolymer in the friction-resistant coating dispersion for a fluorine-containing ion exchange membrane is a perfluorinated ion exchange resin. The perfluorinated ion exchange resin can be one of perfluorinated sulfonic acid ion exchange resin or perfluorinated carboxylic acid ion exchange resin or perfluorinated phosphoric acid ion exchange resin; it may also be a copolymer or blend of at least two of perfluorosulfonic acid ion exchange resin, perfluorocarboxylic acid ion exchange resin and perfluorophosphoric acid ion exchange resin. The perfluorinated ion exchange resin and the ion exchange membrane matrix resin may be the same or different.
Further, the ion exchange capacity of the perfluorinated ion exchange resin is 0.7-1.1 mmol/g. The molecular weight of the perfluorinated ion exchange resin is 18 ten thousand to 28 ten thousand, and the molecular weight distribution is 1.1 to 1.3.
The anti-friction coating prepared from the coating dispersion liquid has the falling rate of less than or equal to 20 percent.
The preparation method of the friction-resistant coating comprises the following steps:
firstly, dissolving a fluorine-containing polymer to obtain a fluorine-containing polymer dispersion liquid; the fluoropolymer may be dissolved using an aqueous alcoholic solution as a solvent;
then, the obtained fluoropolymer dispersion liquid is subjected to homogenization treatment with inorganic particles and additive diethylene glycol and/or diethylene glycol derivatives to form stable coating dispersion liquid; the homogenization treatment adopts the following modes: placing the dispersion liquid of the fluorine-containing polymer, inorganic particles and additive diethylene glycol or diethylene glycol derivatives into a container for sealing, and performing ultrasonic treatment for 2-4 hours at room temperature to form stable coating dispersion liquid.
Finally, the coating dispersion is coated on at least one surface of a fluorine-containing ion exchange membrane base film, and after heat treatment in a high-temperature oven for a certain time, the coating is cured to form a stable friction-resistant coating, and the thickness of the friction-resistant coating is at least 0.5 mu m.
The beneficial effects of the invention are as follows: the raw materials for preparing the friction-resistant coating dispersion liquid of the invention comprise fluoropolymer and inorganic particles, and additives diethylene glycol and/or diethylene glycol derivatives. The addition of the diglycol and/or diglycol derivatives improves the bonding capability between the fluorine-containing polymer in the coating and the ion exchange membrane matrix resin, and further improves the coating firmness of the ion exchange membrane, so that the ion exchange membrane has stronger scratch and scratch resistance in the production, packaging, transportation and application processes, on one hand, the yield and the comprehensive production efficiency of the ion exchange membrane are improved, and on the other hand, the comprehensive use performance of the ion exchange membrane is improved, and great economic and social benefits can be generated.
Drawings
FIG. 1 is a chart showing the apparent coating residue after friction performance testing of the coating with different additives in experimental example 1 of the present invention.
Detailed Description
The following describes the technical scheme of the present invention in detail by examples.
Example 1
The friction-resistant coating dispersion liquid for the fluorine-containing ion exchange membrane consists of perfluorosulfonic acid ion exchange resin with the ion exchange capacity of 0.70mmol/g, zirconia particles with the particle size of 1.0 mu m and an additive diethylene glycol diethyl ether.
Wherein the addition amount of diethylene glycol diethyl ether is 5.0wt% of the mass of the coating dispersion, the mass fraction of the perfluorinated sulfonic acid resin in the dispersion is 60%, and the mass fraction of the zirconia particles is 35%.
The molecular weight of the perfluorinated sulfonic acid resin is 18 ten thousand, and the molecular weight distribution is 1.12.
The method for preparing the friction-resistant coating by adopting the dispersion liquid comprises the following steps:
firstly, dissolving perfluorinated sulfonic acid resin in a water-alcohol mixed solvent to obtain a perfluorinated sulfonic acid resin dispersion liquid;
then, placing the dispersion liquid of the fluorine-containing polymer, zirconia particles and diethylene glycol diethyl ether into a container for sealing, and performing ultrasonic treatment for 2 hours at room temperature to form stable coating dispersion liquid;
finally, the coating dispersion liquid is coated on two surfaces of a fluorine-containing ion exchange membrane base membrane, and the fluorine-containing ion exchange membrane base membrane is subjected to heat treatment in a high-temperature oven for a certain time, so that a stable friction-resistant coating is formed after the coating is solidified, and the thickness of the friction-resistant coating is 1.3 mu m.
The abrasion-resistant coating prepared from the coating dispersion liquid has a falling rate of 11.7%.
Example 2
The friction-resistant coating dispersion liquid for the fluorine-containing ion exchange membrane consists of perfluor phosphoric acid ion exchange resin with the ion exchange capacity of 1.1mmol/g, zirconium nitride particles with the particle size of 20nm, and additives of diethylene glycol and diethylene glycol propyl ether.
Wherein the total addition amount of the additive diethylene glycol and diethylene glycol propyl ether is 0.5wt% of the mass of the coating dispersion, and the mass ratio of the additive diethylene glycol to the diethylene glycol propyl ether is 1:1.
The mass fraction of the perfluorinated phosphoric acid resin is 80 percent, and the mass fraction of the zirconium nitride particles is 19.5 percent. The molecular weight of the perfluorophosphoric acid resin in the dispersion was 28 ten thousand, and the molecular weight distribution was 1.10.
The method for preparing the friction-resistant coating by adopting the dispersion liquid comprises the following steps:
firstly, dissolving a perfluorinated phosphate ion exchange resin in a water-alcohol mixed solvent to obtain a perfluorinated phosphate ion exchange resin dispersion;
then, placing the obtained perfluoro phosphate resin dispersion liquid, zirconium nitride particles, diethylene glycol and diethylene glycol propyl ether into a container for sealing, and performing ultrasonic treatment for 3 hours at room temperature to form stable coating dispersion liquid;
finally, the coating dispersion liquid is coated on the cathode side surface of the fluorine-containing ion exchange membrane base membrane, and the cathode side surface is heat treated in a high-temperature oven for a certain time, so that a stable friction-resistant coating is formed after the coating is solidified, and the thickness of the friction-resistant coating is 2.0 mu m.
An abrasion resistant coating prepared from the coating dispersion had a falling off rate of 15.1%.
Example 3
The friction-resistant coating dispersion liquid for the fluorine-containing ion exchange membrane consists of perfluorocarboxylic acid resin with the ion exchange capacity of 1.07mmol/g, yttrium oxide particles with the particle size of 300nm and additive diglycol.
Wherein the amount of diethylene glycol added is 2.7wt% of the mass of the coating dispersion. The mass fraction of the perfluorocarboxylic acid resin in the dispersion liquid is 70 percent, and the mass fraction of the yttrium oxide particles is 27.3 percent.
The perfluorocarboxylic acid resin had a molecular weight of 20 ten thousand and a molecular weight distribution of 1.21.
The method for preparing the friction-resistant coating by adopting the dispersion liquid comprises the following steps:
firstly, dissolving perfluorocarboxylic acid resin in a hydroalcoholic solvent to obtain a dispersion liquid of the perfluorocarboxylic acid resin;
then, placing the obtained perfluorocarboxylic acid resin dispersion liquid, yttrium oxide particles and diethylene glycol into a container for sealing, and performing ultrasonic treatment for 4 hours at room temperature to form a stable coating dispersion liquid;
finally, the coating dispersion liquid is coated on the surface of the anode side of the fluorine-containing ion exchange membrane base membrane, and the surface is heat treated in a high-temperature oven for a certain time, so that a stable friction-resistant coating is formed after the coating is solidified, and the thickness of the friction-resistant coating is 1.7 mu m.
An abrasion resistant coating prepared from the coating dispersion had a falling off rate of 13.5%.
Example 4
The friction-resistant coating dispersion for the fluorine-containing ion exchange membrane consists of perfluorinated ion polymer with ion exchange capacity of 0.97mmol/g, zirconium oxide and zirconium nitride mixed particles with particle size of 10 mu m and diethylene glycol butyl ether as an additive.
Wherein the perfluorinated ion polymer is formed by blending perfluorocarboxylic acid resin and perfluorophosphoric acid ion exchange resin according to a mass ratio of 4:1. The mass ratio of the zirconia to the zirconia in the zirconia and zirconia mixed particles was 9:1.
The addition amount of diethylene glycol butyl ether is 3.8wt% of the coating dispersion, the mass fraction of perfluorinated ion polymer in the dispersion is 75%, and the mass fraction of mixed particles of zirconium oxide and zirconium nitride is 21.2%.
The molecular weight of the perfluorinated ion polymer is 24w, and the molecular weight distribution is 1.3.
The method for preparing the friction-resistant coating by adopting the dispersion liquid comprises the following steps:
firstly, jointly dissolving perfluorocarboxylic acid resin and perfluorophosphoric acid ion exchange resin in a hydroalcoholic solvent to obtain a perfluoroionic polymer dispersion;
then, placing the obtained perfluorinated ion polymer dispersion liquid, zirconium oxide and zirconium nitride mixed particles and diethylene glycol butyl ether into a container for sealing, and performing ultrasonic treatment for 4 hours at room temperature to form stable coating dispersion liquid;
finally, the coating dispersion liquid is coated on two surfaces of a fluorine-containing ion exchange membrane base membrane, and the fluorine-containing ion exchange membrane base membrane is subjected to heat treatment in a high-temperature oven for a certain time, so that a stable friction-resistant coating is formed after the coating is solidified, and the thickness of the friction-resistant coating is 3.1 mu m.
An abrasion resistant coating prepared from the coating dispersion had a falling off rate of 12.5%.
Comparative example 1
The comparative example 1 differs from example 3 in that: diethylene glycol is not added to the coating raw material, which contains only perfluorocarboxylic acid resin having an ion exchange capacity of 1.07mmol/g and yttrium oxide particles having a particle size of 300 nm.
Comparative example 2
This comparative example 2 differs from example 3 in that: diethylene glycol is replaced with dodecyl ester in the coating raw material. The other is the same.
Comparative example 3
This comparative example 3 differs from example 3 in that: diethylene glycol is replaced by 1, 2-propanediol and cycloacetone in the coating raw material. The other is the same. Wherein the mass ratio of the 1, 2-propylene glycol to the cycloacetone is 4:1.
Comparative example 4
This comparative example 4 differs from example 3 in that: diethylene glycol was replaced with the ishiman film forming aid in the coating stock. The other is the same.
Comparative example 5
This comparative example 5 differs from example 3 in that: diethylene glycol is replaced with glycerol in the coating raw material. The other is the same.
The coating samples obtained in examples 1 to 4 and comparative examples 1 to 5 were subjected to the falling rate test.
1. Test method
The specific operation steps are as follows:
1) Cutting each dried film into strips with the length of 5cm multiplied by 25cm, and soaking in 2wt% NaCl solution for 30min;
2) Taking out the membrane strip, draining water, fixing on a friction tester (Labthink MCJ-01A), and rubbing the surface of the sample membrane strip for 20 times by taking nitrile rubber as a friction pair;
3) Respectively taking samples of a friction area and a non-friction area, immersing the samples in an ethanol solution, carrying out ultrasonic treatment for 4 hours, detecting the inorganic matter content in the coating by XRF, and obtaining respective coating amounts according to the proportion, wherein the coating amount (1-friction area coating amount/non-friction area coating amount) is recorded as the coating falling rate, and the coating is weaker as the coating falling rate is larger.
2. Test results and analysis
The results are shown in Table 1 below, as can be seen from a comparison of the data in Table 1 below: the abrasion resistance of the coating can be significantly improved by the addition of diethylene glycol and/or diethylene glycol derivatives.
Table 1 shedding rate of the coatings obtained in each of examples and comparative examples
Experimental example 1
1. Purpose of experiment
The coatings obtained by adding different assistants to the same coating dispersion were subjected to a friction test, and apparent coating residue was observed.
2. Experimental method
The specific operation is as follows: first, 5wt% of different additives, denoted as samples 1# to 8# were added to the same coating dispersion, respectively, wherein the additives 1# to 8# are shown in Table 2:
TABLE 2
Then taking a perfluorinated ion exchange membrane matrix without a coating, respectively coating equal amounts of samples No. 1-8 on the surface of the perfluorinated ion exchange membrane matrix, preparing a coating, and then carrying out friction test under a load of 500g, wherein the apparent coating residue conditions of different samples after friction are shown in figure 1.
As is evident from FIG. 1, the sample coatings obtained by adding the 3# diethylene glycol, 4# diethylene glycol diethyl ether and 5# diethylene glycol butyl ether auxiliary are less damaged than the other samples.
Claims (9)
1. An antifriction coating dispersion for fluorine-containing ion exchange membranes, comprising inorganic particles, at least one fluorine-containing polymer, characterized in that it further comprises the additives diethylene glycol and/or diethylene glycol derivatives;
the diethylene glycol derivative is diethylene glycol and C x H y (OH) z Wherein x is 4 or less, y=2x+2-z, z is 3 or less;
the total addition amount of the additive diethylene glycol and/or diethylene glycol derivatives is 0.5-5% of the mass of the coating dispersion.
2. The abrasion resistant coating dispersion for a fluorine-containing ion exchange membrane according to claim 1, wherein the diethylene glycol derivative is diethylene glycol diethyl ether, diethylene glycol propyl ether or diethylene glycol butyl ether.
3. The abrasion resistant coating dispersion for a fluorine-containing ion exchange membrane according to claim 1, wherein the particle size of the inorganic particles is 20nm to 10 μm;
the inorganic substance is at least one selected from the group consisting of oxides, hydroxides and nitrides of elements of groups IV-A, IV-B, V-B and III-B.
4. The abrasion resistant coating dispersion for a fluorine-containing ion exchange membrane according to claim 3, wherein the inorganic substance is one or more of zirconia, silica, zirconium nitride and yttria.
5. The friction-resistant coating dispersion for a fluorine-containing ion exchange membrane according to claim 1, wherein the fluorine-containing polymer contains a sulfonic acid group, a carboxylic acid group or a phosphoric acid group.
6. The friction-resistant coating dispersion for a fluorine-containing ion-exchange membrane according to claim 1, wherein the fluorine-containing polymer is a perfluorinated ion-exchange resin.
7. The friction-resistant coating dispersion for a fluorine-containing ion exchange membrane according to claim 6, wherein the ion exchange capacity of the perfluorinated ion exchange resin is 0.7 to 1.1mmol/g.
8. A friction-resistant coating obtained from the coating dispersion according to any one of claims 1 to 7, characterized in that the coating has a shedding rate of less than or equal to 20%.
9. A method of preparing the friction-resistant coating of claim 8, comprising the steps of:
firstly, dissolving a fluorine-containing polymer to obtain a fluorine-containing polymer dispersion liquid;
then, the obtained fluoropolymer dispersion liquid is subjected to homogenization treatment with inorganic particles and additive diethylene glycol and/or diethylene glycol derivatives to form stable coating dispersion liquid;
finally, the coating dispersion is coated on at least one surface of a fluorine-containing ion exchange membrane base membrane, and after curing, a stable friction-resistant coating is formed, wherein the thickness of the friction-resistant coating is at least 0.5 mu m.
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| US20070292622A1 (en) * | 2005-08-04 | 2007-12-20 | Rowley Lawrence A | Solvent containing carbon nanotube aqueous dispersions |
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