CN104624238B - A kind of polyacrylonitrile-radical bionic catalysis fiber and preparation method - Google Patents
A kind of polyacrylonitrile-radical bionic catalysis fiber and preparation method Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 97
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 44
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 46
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 19
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 17
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 13
- 238000010792 warming Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Chemical group 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 7
- 150000001263 acyl chlorides Chemical class 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- -1 macrocycle compound Chemical class 0.000 description 4
- 239000002121 nanofiber Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- IYZPEGVSBUNMBE-UHFFFAOYSA-N 2-[[5-[1-[3-[[carboxylatomethyl(carboxymethyl)azaniumyl]methyl]-4-hydroxy-5-methylphenyl]-3-oxo-2-benzofuran-1-yl]-2-hydroxy-3-methylphenyl]methyl-(carboxymethyl)azaniumyl]acetate Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 IYZPEGVSBUNMBE-UHFFFAOYSA-N 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N Cysteine Chemical class SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000002518 isoindoles Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
A kind of polyacrylonitrile-radical bionic catalysis fiber and preparation method thereof, it is characterized in that：Combined by coordinate bond mode between modified polyacrylonitrile-based fiber and metal phthalocyanine containing mercaptan or imidazole group, its preparation method is：From the polyacrylonitrile fibre containing cyano group, under conditions of 50 100 DEG C, reacted 0.5 4 hours in the NaOH solution that mass fraction is 0.5 20%, make cyano group carboxylated, again under the conditions of 70 90 DEG C, flowed back 4 24 hours in thionyl chloride, thionyl chloride is evaporated after the completion of acyl chloride reaction, add the solution of amineothiot or aminooimidazole, it is warming up to 40 100 DEG C, flow back 2 10 hours, prepare the modified polyacrylonitrile-based fiber containing mercaptan, then the modified polyacrylonitrile-based fiber containing mercaptan is put into 50 100 DEG C of metal phthalocyanine solution and is flowed back 4 12 hours, taking-up is loaded with the pan based fibers of metal phthalocyanine, cyclic washing, 80 100 DEG C of drying are obtained polyacrylonitrile-radical bionic catalysis fiber.The method has equipment simple, and technique is easy, it is easy to the advantages of operating.
Description
Technical field
The present invention relates to a kind of bionic catalysis fiber and preparation method, especially a kind of polyacrylonitrile-radical bionic catalysis fiber
And preparation method, belong to material, chemistry and chemical technology field.
Background technology
Metal phthalocyanine is that the pi-electron Conjugate macrocycle compound that four symmetrical iso-indoles units are constituted is connected by imines bridged bond,
Central metallic ions can be the Determination of multiple metal elements in the periodic table of elements, can introduce many on the phenyl ring of Phthalocyanine periphery
Substitution base is planted, metal phthalocyanine can also be aggregating to form monometallic or many metal poly phthaleins by sharing one or more phenyl ring
Cyanines.Its structure has following characteristics：(1) aromatic series pi-electron is conjugated on whole phthalocyanine ring, and LARGE CONJUGATE MOLECULES is presented the flat of height
Face property, catalytic reaction can occur in the axial location of the plane；(2) aromatic rings had both had the characteristic of electron donor, and with electricity
The characteristic of sub- acceptor；(3) chemical property is highly stable, its acidproof, alkaline-resisting, resistance to water logging, heat-resisting, fast light and resistance to various organic molten
Agent.Features described above, makes them meet the intimate harsh requirement in catalytic process to catalyst, can be used to urge as catalyst
Oxidation, reduction reaction, carbonylation, decomposition reaction, dehalogenation reaction, decarboxylic reaction, polymerisation and Friedel-Crafts reaction
Etc. polytype reaction.The species of central metallic ions and peripheral substituent group, poly phthalocyanine cause change of conjugacy etc.
The catalytic performance of metal phthalocyanine can be influenceed.Additionally, the degree of association of Phthalocyanine is to its catalytic performance in reaction medium
Influence is also larger, and becoming for inactive dimer even polymer is formed because the structure of metal phthalocyanine makes it have in the solution
Gesture, the formation of dimer will reduce the active site of axial coordination, so as to cause catalytic efficiency to be greatly lowered.By the side for loading
Method can effectively improve the recycling performance of metal phthalocyanine.But current most of load-type metal phthalocyanine syntheti c routes are still more
Complexity, and its solvent resistant and resistant to elevated temperatures stability need further raising, accordingly, it would be desirable to develop a kind of simple, gentle system
Preparation Method synthesizes the wider array of high activity loading type metal phthalocyanine catalyst of the scope of application.
The content of the invention
The technical problem to be solved in the present invention is to overcome the shortcomings of above-mentioned background technology, it is therefore an objective to provides polyacrylonitrile-radical and imitates
Raw catalysis fibre and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of polyacrylonitrile-radical bionic catalysis fiber, it is characterized in that：Modified polyacrylonitrile containing mercaptan or imidazole group
Combined by coordinate bond mode between base fiber and metal phthalocyanine, the metal phthalocyanine feature for using has the structure of formula 1, wherein：M is
Iron, cobalt, nickel, manganese, copper, rubidium, zinc, platinum and palladium transition metal ions；R is-H ,-NH2、-Cl、-F、-COOH、-NO2、-
NHCOCH3、-NHSO3H、-SO3Any one in H, including perfluor and perchloro- metal phthalocyanine；Amineothiot (HOOC-R1-SH)
R1It is-CH2-、-CH2CH2-、-CH(COOH)CH2-、-CH2CH2CH2- and-CH2CH2CH2CH2- in any one；Amino miaow
Azoles (NH2-R1-C3H3N2) R2Base is-CH2-、-CH2CH2-、-CH(COOH)CH2-、-CH2CH2CH2- and-CH2CH2CH2CH2- in
Any one,
Described fibre diameter between 0.2-20 μm, pan based fibers shape be grow thread, chopped fiber shape and
Chopped strand shape, can be any fiber containing-CN.
The metal phthalocyanine mass percent of the load is 0.08-8%, the amineothiot of load or the matter of aminooimidazole
Amount fraction is 0.2-15%
A kind of preparation method of polyacrylonitrile-radical bionic catalysis fiber described above, it is characterised in that：From containing cyano group
Polyacrylonitrile fibre, under conditions of 50-100 DEG C, mass fraction for 0.5-20% NaOH solution reaction 0.5-4 it is small
When, make cyano group carboxylated, then under the conditions of 70-90 DEG C, flowed back 4-24 hours in thionyl chloride, steamed after the completion of acyl chloride reaction
Dry thionyl chloride, adds the solution of amineothiot, is warming up to 40-100 DEG C, flows back 2-10 hours, prepares changing containing mercaptan
Property pan based fibers, then will be put into 50-100 DEG C of metal phthalocyanine solution containing the modified polyacrylonitrile-based fiber of mercaptan
Backflow 4-12 hours, taking-up is loaded with the pan based fibers of metal phthalocyanine, and cyclic washing, 80-100 DEG C of drying is obtained poly- third
Alkene itrile group bionic catalysis fiber.
A kind of preparation method of polyacrylonitrile-radical bionic catalysis fiber described above, it is characterised in that：From containing cyano group
Polyacrylonitrile fibre, under conditions of 50-100 DEG C, mass fraction for 0.5-20% NaOH solution reaction 0.5-4 it is small
When, make cyano group carboxylated, then under the conditions of 70-90 DEG C, flowed back 4-24 hours in thionyl chloride, steamed after the completion of acyl chloride reaction
Dry thionyl chloride, adds the solution of aminooimidazole, is warming up to 40-100 DEG C, flows back 2-10 hours, prepares containing imidazole group
Modified polyacrylonitrile-based fiber, the modified polyacrylonitrile-based fiber containing imidazole group is then put into 50-100 DEG C of metal phthalein
Flowed back 4-12 hours in cyanines solution, taking-up is loaded with the polyacrylonitrile fibre of metal phthalocyanine, cyclic washing, 80-100 DEG C of drying system
Obtain polyacrylonitrile-radical bionic catalysis fiber.
The solvent of dissolving amineothiot, aminooimidazole and metal phthalocyanine used can be dimethyl sulfoxide (DMSO), tetrahydrofuran,
Any one in DMF, DMA or 1-METHYLPYRROLIDONE.
The beneficial effects of the invention are as follows：Firstth, the aggregation of metal phthalocyanine can be effectively prevented, it is maintained higher urging
Change activity, using fiber obtained in the method, its catalysis activity is improved than the catalysis activity of the Direct Bonding phthalocyanine on carbon fiber
Decades of times；Secondth, be conducive to overcoming the influence of some unfavorable factors during homogeneous reaction；3rd, by coordinate bond mode
By metal phthalocyanine loaded onto the pan based fibers containing thiol group or imidazole group, be conducive to improving metal phthalocyanine
Catalytic efficiency, reduces the secondary pollution brought by catalyst loss.
The present invention is carrier from polyacrylonitrile fibre, and chemical stability is good, and the catalysis carbon fiber being made has higher
Catalysis activity, separates easily from solution.In preparation process, combined with coordinate bond, with process is simple, simple equipments etc. are excellent
Point.
Obtained catalyzed polypropylene itrile group fiber of the invention can be applied to multiple fields, such as：Organic pollutants are urged
Change oxidation removal, chemical intermediate is catalyzed and synthesized, and in air pernicious gas is removed.Therefore, what prepared by the present invention is poly-
Acrylonitrile group bionic catalysis fiber has a good application prospect.
Brief description of the drawings
Fig. 1 is the process schematic of polyacrylonitrile-radical bionic catalysis fiber producing processes of the present invention.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
And accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is this
A part of embodiment is invented, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art exist
The every other embodiment obtained under the premise of creative work is not made, the scope of protection of the invention is belonged to, should not be managed
Solution is the limitation to the application.
A kind of polyacrylonitrile-radical bionic catalysis fiber, it is by the modified polyacrylonitrile-based fibre containing mercaptan or imidazole group
Dimension is combined between metal phthalocyanine by coordinate bond mode, and the metal phthalocyanine feature for using has the structure of formula 1, wherein：M be iron,
Cobalt, nickel, manganese, copper, rubidium, zinc, platinum and palladium transition metal ions；R is-H ,-NH2、-Cl、-F、-COOH、-NO2、-NHCOCH3、-
NHSO3H、-SO3Any one in H, including perfluor and perchloro- metal phthalocyanine；Amineothiot (HOOC-R1- SH) R1Be-
CH2-、-CH2CH2-、-CH(COOH)CH2-、-CH2CH2CH2- and-CH2CH2CH2CH2- in any one；Aminooimidazole (NH2-
R1-C3H3N2) R2Base is-CH2-、-CH2CH2-、-CH(COOH)CH2-、-CH2CH2CH2- and-CH2CH2CH2CH2- in it is any
One kind,
Between 0.2-20 μm, pan based fibers shape is to grow thread, chopped fiber to fibre diameter of the present invention
Shape and chopped strand shape, can be any fibers containing-CN.The metal phthalocyanine mass percent of the load is 0.08-
8%, the amineothiot of load or the mass fraction of aminooimidazole are 0.2-15%
As shown in figure 1, a kind of preparation method of the polyacrylonitrile-radical bionic catalysis fiber, comprises the concrete steps that：From containing
There is the polyacrylonitrile fibre of cyano group, under conditions of 50-100 DEG C, in mass fraction for the NaOH solution of 0.5-20% is reacted
0.5-4 hours, make cyano group carboxylated, then under the conditions of 70-90 DEG C, flowed back 4-24 hours in thionyl chloride, acyl chloride reaction
After the completion of be evaporated thionyl chloride, add the solution of amineothiot, be warming up to 40-100 DEG C, flow back 2-10 hours, prepare and contain
The modified polyacrylonitrile-based fiber of mercaptan, then the modified polyacrylonitrile-based fiber containing mercaptan is put into 50-100 DEG C of metal phthalein
Flowed back 4-12 hours in cyanines solution, taking-up is loaded with the pan based fibers of metal phthalocyanine, cyclic washing, 80-100 DEG C of drying
Polyacrylonitrile-radical bionic catalysis fiber is obtained.
The preparation method of another polyacrylonitrile-radical bionic catalysis fiber, comprises the concrete steps that：From containing cyano group
Polyacrylonitrile fibre, under conditions of 50-100 DEG C, in mass fraction for the NaOH solution of 0.5-20% is reacted 0.5-4 hours,
Make cyano group carboxylated, then under the conditions of 70-90 DEG C, flowed back 4-24 hours in thionyl chloride, be evaporated after the completion of acyl chloride reaction
Thionyl chloride, adds the solution of aminooimidazole, is warming up to 40-100 DEG C, flows back 2-10 hours, prepares containing imidazole group
Modified polyacrylonitrile-based fiber, then the modified polyacrylonitrile-based fiber containing imidazole group is put into 50-100 DEG C of metal phthalocyanine
Flowed back 4-12 hours in solution, taking-up is loaded with the polyacrylonitrile fibre of metal phthalocyanine, cyclic washing, 80-100 DEG C of drying is obtained
Polyacrylonitrile-radical bionic catalysis fiber.
The solvent of dissolving amineothiot, aminooimidazole and metal phthalocyanine used can be dimethyl sulfoxide (DMSO), tetrahydrofuran,
Any one in DMF, DMA or 1-METHYLPYRROLIDONE.
Embodiment 1
A kind of preparation method of polyacrylonitrile-radical bionic catalysis fiber, it is comprised the following steps that：
15g polyacrylonitrile fibres are weighed, under conditions of 95 DEG C, 2 is stirred with the NaOH solution that mass fraction is 10% small
When, after drying again under the conditions of 85 DEG C, flowed back 20 hours in 400mL thionyl chlorides, thionyl chloride is evaporated after the completion of reaction,
Enter the DMF solution of the aminoothyl mercaptan of 0.3mol/L, be warming up to 60 DEG C, flow back 8 hours, then will grafting
Backflow 10 is small during the polyacrylonitrile fibre of aminoothyl mercaptan is put into the tetrahydrofuran solution of the cobalt phthalocyanine of 80 DEG C of 0.2mmol/L
When, taking-up is loaded with the polyacrylonitrile fibre of cobalt phthalocyanine, colourless to solution with solvent cyclic washing, and 80 DEG C of drying are obtained polypropylene
Itrile group bionic catalysis fiber.
Embodiment 2
A kind of preparation method of polyacrylonitrile-radical bionic catalysis fiber, it is comprised the following steps that：
5g polyacrylonitrile nanofibers are weighed, under conditions of 95 DEG C, 1 is stirred with the NaOH solution that mass fraction is 10%
Hour, after drying again under the conditions of 85 DEG C, flowed back 10 hours in 200mL thionyl chlorides, thionyl chloride is evaporated after the completion of reaction,
The DMF solution of the aminoothyl mercaptan of 0.3mol/L is poured into, 60 DEG C are warming up to, flowed back 8 hours, then will connect
The polyacrylonitrile nanofiber of branch aminoothyl mercaptan flows back in being put into the tetrahydrofuran solution of the iron-phthalocyanine of 80 DEG C of 0.2mmol/L
8 hours, taking-up was loaded with the polyacrylonitrile nanofiber of iron-phthalocyanine, colourless to solution with solvent cyclic washing, 90 DEG C of drying systems
Obtain polyacrylonitrile-radical bionic catalysis fiber.
Embodiment 3
A kind of preparation method of polyacrylonitrile-radical bionic catalysis fiber, it is comprised the following steps that：
10g polyacrylonitrile fibres are weighed, under conditions of 85 DEG C, 3 is stirred with the NaOH solution that mass fraction is 15% small
When, after drying again under the conditions of 85 DEG C, flowed back 20 hours in 400mL thionyl chlorides, thionyl chloride is evaporated after the completion of reaction,
Enter the DMF solution of 5- (2- amino -2- carboxy ethyls) imidazoles of 0.3mol/L, be warming up to 60 DEG C, backflow 8
Hour, then the polyacrylonitrile fibre for being grafted 5- (2- amino -2- carboxy ethyls) imidazoles is put into the cobalt of 80 DEG C of 0.2mmol/L
Flowed back 10 hours in the tetrahydrofuran solution of phthalocyanine, taking-up is loaded with the polyacrylonitrile fibre of cobalt phthalocyanine, uses solvent cyclic washing
Colourless to solution, 80 DEG C of drying are obtained polyacrylonitrile-radical bionic catalysis fiber.
Embodiment 4
A kind of preparation method of polyacrylonitrile-radical bionic catalysis fiber, it is comprised the following steps that：
6g polyacrylonitrile fibres are weighed, under conditions of 80 DEG C, 2 is stirred with the NaOH solution that mass fraction is 12% small
When, after drying again under the conditions of 85 DEG C, flowed back 16 hours in 150mL thionyl chlorides, thionyl chloride is evaporated after the completion of reaction,
Enter the DMF solution of 5- (2- amino-ethyls) imidazoles of 0.3mol/L, be warming up to 70 DEG C, flow back 6 hours, so
The polyacrylonitrile fibre for being grafted 5- (2- amino-ethyls) imidazoles is put into the tetrahydrofuran of the manganese phthalocyanine of 80 DEG C of 0.2mmol/L afterwards
Flowed back 12 hours in solution, taking-up is loaded with the polyacrylonitrile fibre of manganese phthalocyanine, colourless to solution with solvent cyclic washing, 80 DEG C
Drying is obtained polyacrylonitrile-radical bionic catalysis fiber.
Embodiment 5
A kind of preparation method of polyacrylonitrile-radical bionic catalysis fiber, it is comprised the following steps that：
20g polyacrylonitrile fibres are weighed, under conditions of 95 DEG C, 0.5 is stirred with the NaOH solution that mass fraction is 10%
Hour, after drying again under the conditions of 85 DEG C, flowed back 12 hours in 400mL thionyl chlorides, thionyl chloride is evaporated after the completion of reaction,
The DMF solution of the aminoothyl mercaptan of 0.3mol/L is poured into, 60 DEG C are warming up to, flowed back 8 hours, then will connect
Backflow 10 is small during the polyacrylonitrile fibre of branch aminoothyl mercaptan is put into the tetrahydrofuran solution of the iron-phthalocyanine of 70 DEG C of 0.2mmol/L
When, taking-up is loaded with the polyacrylonitrile fibre of iron-phthalocyanine, colourless to solution with solvent cyclic washing, and 80 DEG C of drying are obtained polypropylene
Itrile group bionic catalysis fiber.
Embodiment 6
A kind of preparation method of polyacrylonitrile-radical bionic catalysis fiber, it is comprised the following steps that：
9g polyacrylonitrile nanofibers are weighed, under conditions of 95 DEG C, is stirred with the NaOH solution that mass fraction is 6%
0.5 hour, after drying again under the conditions of 80 DEG C, flowed back 15 hours in 300mL thionyl chlorides, dichloro is evaporated after the completion of reaction sub-
Sulfone, pours into the DMF solution of the 2- amino -2- carboxyl ethyl mercaptans of 0.3mol/L, is warming up to 65 DEG C, and backflow 8 is small
When, then the polyacrylonitrile fibre for being grafted 2- amino -2- carboxyl ethyl mercaptans is put into the four of the ZnPc of 80 DEG C of 0.2mmol/L
Flowed back 12 hours in hydrogen tetrahydrofuran solution, taking-up is loaded with the polyacrylonitrile fibre of ZnPc, with solvent cyclic washing to solution without
Color, 95 DEG C of drying are obtained polyacrylonitrile-radical bionic catalysis fiber
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；To the greatest extent
Pipe has been described in detail to the present invention with reference to the foregoing embodiments, it will be understood by those within the art that：It is still
Technical scheme described in foregoing embodiments can be modified, or which part technical characteristic is equally replaced
Change；And these modifications or replacement, do not make the essence of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution
God and scope.
Claims (6)
1. a kind of polyacrylonitrile-radical bionic catalysis fiber, it is characterized in that：It is modified polyacrylonitrile-based containing mercaptan or imidazole group
Combined by coordinate bond mode between fiber and metal phthalocyanine, the metal phthalocyanine feature for using has the structure of formula 1, wherein：M is
Iron, cobalt, nickel, manganese, copper, rubidium, zinc, platinum and palladium transition metal ions；R is-H ,-NH2、-Cl、-F、-COOH、-NO2、-
NHCOCH3、-NHSO3H、-SO3Any one in H；Amineothiot HOOC-R1The R of-SH1It is-CH2-、-CH2CH2-、-CH
(COOH)CH2-、-CH2CH2CH2- and-CH2CH2CH2CH2- in any one；Aminooimidazole NH2-R1-C3H3N2R2Base is-
CH2-、-CH2CH2-、-CH(COOH)CH2-、-CH2CH2CH2- and-CH2CH2CH2CH2- in any one,
2. polyacrylonitrile-radical bionic catalysis fiber according to claim 1, it is characterised in that described fibre diameter exists
Between 0.2-20 μm, pan based fibers shape is to grow thread or chopped fiber shape, can be any fiber containing-CN.
3. polyacrylonitrile-radical bionic catalysis fiber according to claim 1 and 2, it is characterised in that the metal phthalocyanine matter of load
Amount percentage is 0.08-8%, and the amineothiot of load or the mass fraction of aminooimidazole are 0.2-15%.
4. a kind of preparation method of the polyacrylonitrile-radical bionic catalysis fiber as described in claim 1 or 2 or 3, it is characterised in that：Choosing
With the polyacrylonitrile fibre containing cyano group, under conditions of 50-100 DEG C, in mass fraction for the NaOH solution of 0.5-20% is anti-
Answer 0.5-4 hours, make cyano group carboxylated, then under the conditions of 70-90 DEG C, flowed back 4-24 hours in thionyl chloride, chloride is anti-
Thionyl chloride is evaporated after the completion of answering, the solution of amineothiot is added, 40-100 DEG C is warming up to, flowed back 2-10 hours, prepared
Modified polyacrylonitrile-based fiber containing mercaptan, then the modified polyacrylonitrile-based fiber containing mercaptan is put into 50-100 DEG C of metal
Flowed back 4-12 hours in phthalocyanine solution, taking-up is loaded with the pan based fibers of metal phthalocyanine, cyclic washing, 80-100 DEG C of baking
It is drying to obtain polyacrylonitrile-radical bionic catalysis fiber.
5. a kind of preparation method of the polyacrylonitrile-radical bionic catalysis fiber as described in claim 1 or 2 or 3, it is characterised in that：Choosing
With the polyacrylonitrile fibre containing cyano group, under conditions of 50-100 DEG C, in mass fraction for the NaOH solution of 0.5-20% is anti-
Answer 0.5-4 hours, make cyano group carboxylated, then under the conditions of 70-90 DEG C, flowed back 4-24 hours in thionyl chloride, chloride is anti-
Thionyl chloride is evaporated after the completion of answering, the solution of aminooimidazole is added, 40-100 DEG C is warming up to, flowed back 2-10 hours, prepared
Modified polyacrylonitrile-based fiber containing imidazole group, is then put into 50-100 by the modified polyacrylonitrile-based fiber containing imidazole group
DEG C metal phthalocyanine solution in flow back 4-12 hour, take out and be loaded with the polyacrylonitrile fibre of metal phthalocyanine, cyclic washing, 80-
100 DEG C of drying are obtained polyacrylonitrile-radical bionic catalysis fiber.
6. according to claim 4 or 5 polyacrylonitrile-radical bionic catalysis fiber preparation method, it is characterised in that used is molten
Solution amineothiot, the solvent of aminooimidazole and metal phthalocyanine are dimethyl sulfoxide (DMSO), tetrahydrofuran, DMF, N,
Any one in N- dimethylacetylamides or 1-METHYLPYRROLIDONE.
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| JP2001303437A (en) * | 2000-04-24 | 2001-10-31 | Tokuji Yokozeki | Itch preventing, antipruritic and antiflash fiber and method for producing the same |
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| CN103721747A (en) * | 2013-12-13 | 2014-04-16 | 浙江理工大学 | Catalytic carbon fibers and preparation method |
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