CN107174973A - A kind of preparation method of the plain composite membrane of graphene fiber - Google Patents
A kind of preparation method of the plain composite membrane of graphene fiber Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000835 fiber Substances 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 229920002678 cellulose Polymers 0.000 claims abstract description 17
- 239000001913 cellulose Substances 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001408 amides Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000020 Nitrocellulose Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229920001220 nitrocellulos Polymers 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- 239000005018 casein Substances 0.000 claims description 4
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 4
- 235000021240 caseins Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 graphite Alkene Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 210000004885 white matter Anatomy 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- 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
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a kind of preparation method of the plain composite membrane of graphene fiber, the present invention by amination modified, then handles graphene oxide carboxylated cellulose, then blended cross linking, obtain the good compelx coating of dispersing uniformity in HPMA, acetone soln, the present invention obtains hydrophilic acid amides, improves the good hydrophilic property of compelx coating by amidatioon cross-linking reaction, the surface strength and toughness of film are improved simultaneously, good weatherability, not cracky, combination property is superior.
Description
Technical field
The invention belongs to film applications, and in particular to a kind of preparation method of the plain composite membrane of graphene fiber.
Background technology
Nitrocellulose, is the product of cellulose and nitric acid esterification, with good film forming, is earliest in the world
One of high molecular polymer for preparing film, in recent years, due to the macromolecule feature of nitrocellulose in itself, its application by
Gradually apply from being separated by filtration to be transferred in terms of the higher bioanalysis of added value, this mainly has benefited from nitrocellulose to egg
The non-specific adsorption ability of the materials such as white matter.On the other hand, need film that there is parent in the application of quick diagnosis class product
It is aqueous, propose requirement due to the hydrophobicity of nitrocellulose itself, and to the post processing of film；
Because the thickness of graphene is in nanoscale, mutual group would generally occur for not surface treated graphene powder or slurry
Gather to drop low-surface-energy, and in actual applications, the graphene reunited together is can not to form effective under macro-scale
Conductive network is overlapped mutually the membrane structure for constituting densification, and both forms are two kinds of main shapes of graphene macroscopic view application
Formula.Therefore, it is the committed step for realizing graphene application to realize good solution dispersion.So-called good disperses, and refers to graphite
Alkene lamella is all stabilized with independent lamella in the solution, and with higher concentration.Graphene is a kind of chemical inertness
Very strong material, research shows that the liquid phase substance that can be produced with it compared with strong interaction only has superpower acid, such as oleum
Acid, chlorosulfonic acid etc., but with certain danger and harsh is required to use environment due to this kind of material, even if thus graphene
It can realize wherein effectively scattered, it is also difficult to realize the extensive application based on this kind of solution.In addition, what is be currently known is conventional
Solvent is difficult to the effectively scattered of high-quality graphene；
Having been reported that at present can realize that the scattered solvent of graphene transient stability mainly has 1-METHYLPYRROLIDONE, dimethyl Malaysia
Acid anhydrides and dichloroethanes etc., but dispersible concentration highest is only capable of reaching 0.1%, it is scattered for high-quality graphene in report at present
Common method be to utilize surfactant, such as lauryl sodium sulfate, neopelex, or linear solvable high score
Sub- material, such as polyvinylpyrrolidone, cellulose derivative, polyvinyl alcohol, realize graphene conventional as dispersing aid
Scattered in solvent, such as water, ethanol, dispersion concentration can be more than 1%, but preparing graphene using this dispersion liquid, such as
Graphene film etc., it will usually cause liquid phase be molded after dispersant remnants and be difficult to remove.
Therefore, the purpose of the present invention is exactly uniform and stable thin of formation in order to graphene is effectively blended with cellulose
Film, to improve the hydrophily of film surface, while improving film surface intensity, improves the toughness of the plain film of traditional fibre, expands
It uses scope.
The content of the invention
The purpose of the present invention is exactly the uniform and stable film of formation in order to which graphene is effectively blended with cellulose, with
The hydrophily of film surface is improved, while improving film surface intensity, the toughness of the plain film of traditional fibre is improved, expands it and use
There is provided a kind of preparation method of the plain composite membrane of graphene fiber for scope.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of the plain composite membrane of graphene fiber, comprises the following steps：
（1）The graphene of 3-5 parts by weight is taken, in the mixed acid solution for being added to 25-30 times of its weight, rise temperature is 50-60 DEG C,
Ultrasonic 1-2 hours, precipitation is washed in filtering, is dried completely at 100-110 DEG C of vacuum, is obtained graphene oxide；
（2）The nitrocellulose of 110-120 parts by weight is taken, in the absolute ethyl alcohol for being added to 10-14 times of its weight, is stirred,
The APTES of 3-4 parts by weight is added, rise temperature is 60-65 DEG C, insulated and stirred 2-3 hours, distillation
Ethanol is removed, air drying obtains amino cellulose；
（3）The initiator of 0.7-1 parts by weight is taken, in the deionized water for being added to 20-30 times of its weight, is stirred；
（4）Maleic anhydride, the casein mixing of 1-2 parts by weight of 30-35 parts by weight are taken, 7-10 times of compound weight is added to
In deionized water, stir, be sent in reactor, be passed through nitrogen, regulation temperature of reaction kettle is 70-75 DEG C, is added dropwise above-mentioned
Stirring reaction 2-3 hours after initiator solution, completion of dropping, discharging obtains polyamide solution；
（5）Above-mentioned graphene oxide is taken, is mixed with the p-methyl benzenesulfonic acid of 3-4 parts by weight, the insulated and stirred 20- at 80-90 DEG C
30 minutes, mix, be sent in 55-60 DEG C of water bath with thermostatic control with above-mentioned amino cellulose, insulated and stirred 1-2 hours, discharging,
It is added in above-mentioned polyamide solution, it is ultrasonic 10-15 minutes, obtain crosslinked amide dispersion liquid；
（6）Above-mentioned crosslinked amide dispersion liquid is taken, the acetone, the Arlacel-80 of 1-2 parts by weight with 20-30 parts by weight are mixed, stirring is equal
Even, deaeration filtering obtains preparation liquid；
（7）Above-mentioned preparation liquid is taken, is coated on the stainless steel band continuously run, the wet-film thickness of coating is 100-600 μm,
Dried at 60-70 DEG C, produce the plain composite membrane of the graphene fiber.
Described mixed acid solution is that volume ratio is 5-7:The mixed solution of 1 90-95% sulfuric acid, 94-97% nitric acid.
Described initiator is one kind in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate.
Advantages of the present invention：
The present invention, by amino silane modified, obtains amino cellulose first by cellulose, then using maleic anhydride as monomer,
It polymerize under initiator effect, obtains polyamide solution；Then graphene oxide is handled by p-methyl benzenesulfonic acid, obtains carboxyl
Graphene oxide, is then being mixed into row amidation process with amino cellulose, is being subsequently dispersed in polyamide solution, then with
Acetone mixed dissolution, coating film forming；
Graphene oxide carboxylated by amination modified, then handled, then blended cross linking, obtained by the present invention by cellulose
The good compelx coating of dispersing uniformity in HPMA, acetone soln, the present invention obtains parent by amidatioon cross-linking reaction
Aqueous acid amides, improves the good hydrophilic property of compelx coating, while the surface strength and toughness of film are improved, good weatherability,
Not cracky, combination property is superior.
Embodiment
Embodiment 1
A kind of preparation method of the plain composite membrane of graphene fiber, comprises the following steps：
（1）The graphene of 5 parts by weight is taken, in the mixed acid solution for being added to 30 times of its weight, rise temperature is 60 DEG C, and ultrasound 2 is small
When, precipitation is washed in filtering, is dried completely at 110 DEG C of vacuum, is obtained graphene oxide；
（2）The nitrocellulose of 120 parts by weight is taken, in the absolute ethyl alcohol for being added to 14 times of its weight, is stirred, 4 weights are added
The APTES of part is measured, rise temperature is 65 DEG C, ethanol is distilled off in insulated and stirred 3 hours, and normal temperature is done
It is dry, obtain amino cellulose；
（3）The initiator of 1 parts by weight is taken, in the deionized water for being added to 30 times of its weight, is stirred；
（4）Maleic anhydride, the casein mixing of 2 parts by weight of 35 parts by weight are taken, the deionization of 10 times of compound weight is added to
In water, stir, be sent in reactor, be passed through nitrogen, regulation temperature of reaction kettle is 75 DEG C, above-mentioned initiator is added dropwise water-soluble
Stirring reaction 3 hours after liquid, completion of dropping, discharging, obtain polyamide solution；
（5）Above-mentioned graphene oxide is taken, is mixed with the p-methyl benzenesulfonic acid of 4 parts by weight, insulated and stirred 30 minutes at 90 DEG C, with
Above-mentioned amino cellulose mixing, in the water bath with thermostatic control for being sent to 60 DEG C, insulated and stirred 2 hours, discharging is added to above-mentioned polyamides
In amine aqueous solution, ultrasound 15 minutes obtains crosslinked amide dispersion liquid；
（6）Above-mentioned crosslinked amide dispersion liquid is taken, the acetone, the Arlacel-80 of 2 parts by weight with 30 parts by weight are mixed, and are stirred, taken off
Bubble filtering, obtains preparation liquid；
（7）Above-mentioned preparation liquid is taken, is coated on the stainless steel band continuously run, the wet-film thickness of coating is 100-600 μm,
Dried at 70 DEG C, produce the plain composite membrane of the graphene fiber.
Described mixed acid solution is volume ratio -7:1 95% sulfuric acid, the mixed solution of 97% nitric acid.
Described initiator is potassium peroxydisulfate.
Embodiment 2
A kind of preparation method of the plain composite membrane of graphene fiber, comprises the following steps：
（1）The graphene of 3 parts by weight is taken, in the mixed acid solution for being added to 25 times of its weight, rise temperature is 50 DEG C, and ultrasound 1 is small
When, precipitation is washed in filtering, is dried completely at 100 DEG C of vacuum, is obtained graphene oxide；
（2）The nitrocellulose of 110 parts by weight is taken, in the absolute ethyl alcohol for being added to 10 times of its weight, is stirred, 3 weights are added
The APTES of part is measured, rise temperature is 60 DEG C, ethanol is distilled off in insulated and stirred 2 hours, and normal temperature is done
It is dry, obtain amino cellulose；
（3）The initiator of 0.7 parts by weight is taken, in the deionized water for being added to 20 times of its weight, is stirred；
（4）Maleic anhydride, the casein mixing of 1 parts by weight of 30 parts by weight are taken, the deionized water of 7 times of compound weight is added to
In, stir, be sent in reactor, be passed through nitrogen, regulation temperature of reaction kettle is 70 DEG C, above-mentioned initiator is added dropwise water-soluble
Stirring reaction 2-3 hours after liquid, completion of dropping, discharging obtains polyamide solution；
（5）Above-mentioned graphene oxide is taken, is mixed with the p-methyl benzenesulfonic acid of 3 parts by weight, insulated and stirred 20 minutes at 80 DEG C, with
Above-mentioned amino cellulose mixing, in the water bath with thermostatic control for being sent to 55 DEG C, insulated and stirred 1 hour, discharging is added to above-mentioned polyamides
In amine aqueous solution, ultrasound 10 minutes obtains crosslinked amide dispersion liquid；
（6）Above-mentioned crosslinked amide dispersion liquid is taken, the acetone, the Arlacel-80 of 1 parts by weight with 20 parts by weight are mixed, and are stirred, taken off
Bubble filtering, obtains preparation liquid；
（7）Above-mentioned preparation liquid is taken, is coated on the stainless steel band continuously run, the wet-film thickness of coating is 100-600 μm,
Dried at 60 DEG C, produce the plain composite membrane of the graphene fiber.
Described mixed acid solution is that volume ratio is 5:1 90% sulfuric acid, the mixed solution of 94% nitric acid.
Described initiator is ammonium persulfate.
Claims (3)
1. the preparation method of the plain composite membrane of a kind of graphene fiber, it is characterised in that comprise the following steps：
（1）The graphene of 3-5 parts by weight is taken, in the mixed acid solution for being added to 25-30 times of its weight, rise temperature is 50-60 DEG C,
Ultrasonic 1-2 hours, precipitation is washed in filtering, is dried completely at 100-110 DEG C of vacuum, is obtained graphene oxide；
（2）The nitrocellulose of 110-120 parts by weight is taken, in the absolute ethyl alcohol for being added to 10-14 times of its weight, is stirred,
The APTES of 3-4 parts by weight is added, rise temperature is 60-65 DEG C, insulated and stirred 2-3 hours, distillation
Ethanol is removed, air drying obtains amino cellulose；
（3）The initiator of 0.7-1 parts by weight is taken, in the deionized water for being added to 20-30 times of its weight, is stirred；
（4）Maleic anhydride, the casein mixing of 1-2 parts by weight of 30-35 parts by weight are taken, 7-10 times of compound weight is added to
In deionized water, stir, be sent in reactor, be passed through nitrogen, regulation temperature of reaction kettle is 70-75 DEG C, is added dropwise above-mentioned
Stirring reaction 2-3 hours after initiator solution, completion of dropping, discharging obtains polyamide solution；
（5）Above-mentioned graphene oxide is taken, is mixed with the p-methyl benzenesulfonic acid of 3-4 parts by weight, the insulated and stirred 20- at 80-90 DEG C
30 minutes, mix, be sent in 55-60 DEG C of water bath with thermostatic control with above-mentioned amino cellulose, insulated and stirred 1-2 hours, discharging,
It is added in above-mentioned polyamide solution, it is ultrasonic 10-15 minutes, obtain crosslinked amide dispersion liquid；
（6）Above-mentioned crosslinked amide dispersion liquid is taken, the acetone, the Arlacel-80 of 1-2 parts by weight with 20-30 parts by weight are mixed, stirring is equal
Even, deaeration filtering obtains preparation liquid；
（7）Above-mentioned preparation liquid is taken, is coated on the stainless steel band continuously run, the wet-film thickness of coating is 100-600 μm,
Dried at 60-70 DEG C, produce the plain composite membrane of the graphene fiber.
2. the preparation method of the plain composite membrane of a kind of graphene fiber according to claim 1, it is characterised in that described is mixed
Acid solution is that volume ratio is 5-7:The mixed solution of 1 90-95% sulfuric acid, 94-97% nitric acid.
3. the preparation method of the plain composite membrane of a kind of graphene fiber according to claim 1, it is characterised in that described draws
Hair agent is one kind in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108963231A (en) * | 2018-07-23 | 2018-12-07 | 戚明海 | Modified lithium-sulphur cell positive electrode active material of a kind of graphene and preparation method thereof |
| CN109096750A (en) * | 2018-07-18 | 2018-12-28 | 桐城市明丽碳化硼制品有限公司 | A kind of graphene film and preparation method thereof |
| CN109859879A (en) * | 2019-03-06 | 2019-06-07 | 毛红玲 | A kind of high-performance conductive film and its processing method based on graphene |
| CN112047795A (en) * | 2020-08-28 | 2020-12-08 | 西安近代化学研究所 | Preparation method of graphene oxide/nitrocotton compound |
| CN115582094A (en) * | 2021-07-05 | 2023-01-10 | 中国石油天然气集团有限公司 | Adsorption film and preparation method and application thereof |
| CN117000045A (en) * | 2023-06-01 | 2023-11-07 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane for removing heavy metals and preparation method thereof |
| CN117186347A (en) * | 2023-08-14 | 2023-12-08 | 东莞市腾崴塑胶制品有限公司 | Modified bamboo fiber sponge and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150165389A1 (en) * | 2011-06-17 | 2015-06-18 | Battelle Memorial Institute | Forward Osmosis, Reverse Osmosis, and Nano/Micro Filtration Membrane Structures |
| CN105921031A (en) * | 2016-05-15 | 2016-09-07 | 高学理 | Carboxylic oxidized graphene and method for modifying organic release film by means of same |
| US20160303518A1 (en) * | 2015-04-15 | 2016-10-20 | Korea Research Institute Of Chemical Technology | Nanocomposite ultrafiltration membrane containing graphene oxide or reduced graphene oxide and preparation method thereof |
| CN106076132A (en) * | 2016-06-27 | 2016-11-09 | 天津工业大学 | A kind of graphene oxide modified polyamide composite nanometer filtering film and preparation method thereof |
| CN106700110A (en) * | 2017-01-09 | 2017-05-24 | 东北林业大学 | Preparation method of graphene oxide/nano cellulose/polyvinyl alcohol composite film |
-
2017
- 2017-06-30 CN CN201710521346.XA patent/CN107174973B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150165389A1 (en) * | 2011-06-17 | 2015-06-18 | Battelle Memorial Institute | Forward Osmosis, Reverse Osmosis, and Nano/Micro Filtration Membrane Structures |
| US20160303518A1 (en) * | 2015-04-15 | 2016-10-20 | Korea Research Institute Of Chemical Technology | Nanocomposite ultrafiltration membrane containing graphene oxide or reduced graphene oxide and preparation method thereof |
| CN105921031A (en) * | 2016-05-15 | 2016-09-07 | 高学理 | Carboxylic oxidized graphene and method for modifying organic release film by means of same |
| CN106076132A (en) * | 2016-06-27 | 2016-11-09 | 天津工业大学 | A kind of graphene oxide modified polyamide composite nanometer filtering film and preparation method thereof |
| CN106700110A (en) * | 2017-01-09 | 2017-05-24 | 东北林业大学 | Preparation method of graphene oxide/nano cellulose/polyvinyl alcohol composite film |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096750A (en) * | 2018-07-18 | 2018-12-28 | 桐城市明丽碳化硼制品有限公司 | A kind of graphene film and preparation method thereof |
| CN108963231A (en) * | 2018-07-23 | 2018-12-07 | 戚明海 | Modified lithium-sulphur cell positive electrode active material of a kind of graphene and preparation method thereof |
| CN109859879A (en) * | 2019-03-06 | 2019-06-07 | 毛红玲 | A kind of high-performance conductive film and its processing method based on graphene |
| CN112047795A (en) * | 2020-08-28 | 2020-12-08 | 西安近代化学研究所 | Preparation method of graphene oxide/nitrocotton compound |
| CN112047795B (en) * | 2020-08-28 | 2022-04-19 | 西安近代化学研究所 | Preparation method of graphene oxide/nitrocotton compound |
| CN115582094A (en) * | 2021-07-05 | 2023-01-10 | 中国石油天然气集团有限公司 | Adsorption film and preparation method and application thereof |
| CN115582094B (en) * | 2021-07-05 | 2024-04-19 | 中国石油天然气集团有限公司 | Adsorption film and preparation method and application thereof |
| CN117000045A (en) * | 2023-06-01 | 2023-11-07 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane for removing heavy metals and preparation method thereof |
| CN117000045B (en) * | 2023-06-01 | 2024-02-20 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane for removing heavy metals and preparation method thereof |
| CN117186347A (en) * | 2023-08-14 | 2023-12-08 | 东莞市腾崴塑胶制品有限公司 | Modified bamboo fiber sponge and preparation method thereof |
| CN117186347B (en) * | 2023-08-14 | 2024-02-20 | 东莞市腾崴塑胶制品有限公司 | Modified bamboo fiber sponge and preparation method thereof |
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