CN103966851B - A kind of functional AOPAN nanofiber and preparation method thereof - Google Patents
A kind of functional AOPAN nanofiber and preparation method thereof Download PDFInfo
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- CN103966851B CN103966851B CN201410218848.1A CN201410218848A CN103966851B CN 103966851 B CN103966851 B CN 103966851B CN 201410218848 A CN201410218848 A CN 201410218848A CN 103966851 B CN103966851 B CN 103966851B
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Abstract
The present invention provides a kind of functional AOPAN nanofiber and preparation method thereof, utilize atomic radicals polymerization technique grafted methacrylic acid hydroxyethyl ester (HEMA) molecular brush on AOPAN nanofiber surface, the functional nano fibre morphology prepared is stable, porosity is high, specific surface area is big, and a large amount of active group is contained on surface；Preparation method simplifies the catalyst system and catalyzing of reaction, and the response time is short.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, be specifically related to a kind of functional AOPAN nanofiber and preparation method thereof.
Background technology
Utilizing the high polymer containing functional groups is matrix, and by MOLECULE DESIGN, synthesis has the functional of specified chemical structure
Macromolecular material is always the research emphasis of material science.Atom transfer radical polymerization (ATRP) utilize transition metal ions with
Forming catalyst system and catalyzing to electron donor ligand, by the initiation of free radical, functional monomer polymerization is prepared specific macromolecular material, is
A kind of reaction condition is gentle, the novel synthetic technology of operation relative ease.
ATRP technology grafting HEMA molecular brush is utilized to need matrix surface to have hydroxyl isoreactivity group as priming site, currently
This type of modification is all that this type of matrix specific surface area is little, it is possible to provide draw using the conventional cellulose fibre of yardstick, paper etc. as matrix
Send out and the avtive spot of grafting is few.Nanofiber has the biggest specific surface area, but the nanofiber preparation technology of cellulose base is still
Immature；The polyvinyl alcohol (PVA) of rich surface hydroxyl is although nanofiber is easily prepared, and has bigger specific surface area,
But this matrix is in process of grafting, morphosis is unstable, loses nanofiber form the most completely.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of functional AOPAN nanofiber and preparation method thereof, present invention profit
By atomic radicals polymerization technique grafted methacrylic acid hydroxyethyl ester (HEMA) molecular brush on AOPAN nanofiber surface, system
The functional nano fibre morphology obtained is stable, and porosity is high, and specific surface area is big, and a large amount of active group is contained on surface；Preparation method
Simplifying the catalyst system and catalyzing of reaction, the response time is short.
The technical solution used in the present invention is:
A kind of functional AOPAN nanofiber, by AOPAN nanofiber surface grafted methacrylic acid hydroxyethyl ester (HEMA)
Molecular brush is constituted, and its structural representation formula is:
Wherein: n=30-50.
A kind of preparation method of functional AOPAN nanofiber, step includes:
A, by AOPAN nanofiber dipping more than 5min in the oxolane (THF), be subsequently adding 2-bromo-2-methyl-prop
Acylbromide (2-BIB) and triethylamine, 30-40 DEG C of heating in water bath 3-4h after mix homogeneously, divides reacted AOPAN nanofiber
Not Yong THF and water washing, vacuum drying, prepare free radical cause AOPAN nanofiber；Described AOPAN nanofiber,
2-bromo-2-methyl-prop acylbromide (2-BIB) and triethylamine concentration in oxolane are respectively 0.3-0.5g/50mL, 55-65
μL/50mL、70μL/50mL。
B into, CuCl is poured the 1,1,4,7,10,10-hexamethyl of freezing deoxygenation after mixing with the ratio of volume ratio 0.3-0.5:24
In triethylene tetramine (HMTETA) and DMF (DMF) mixture, stirring and evenly mixing, it is subsequently adding freezing and removes
Methacrylate (HEMA) after oxygen prepares mixed solution, described CuCl, DMF, methyl
The ratio of hydroxyethyl acrylate is 0.08-0.1g:24mL:24mL；
Described deoxidation method for will be equipped with 1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl triethylene tetramines (HMTETA) and N, N-dimethyl methyl
The container of amide (DMF) mixture and container more than the liquid nitrogen freezing 5min equipped with methacrylate, then
Container after freezing is thawed in the glove box of evacuation, repeated freezing and thawing process more than 2 times.
The AOPAN nanofiber that C, free radical step A prepared cause is put in the mixed solution that step B prepares, reaction
After 40-60min, nanofiber taking-up is clean with washes of absolute alcohol, dry prepared functional AOPAN nanofiber；Institute
State step A prepare free radical cause AOPAN nanofiber and step B prepare mixed solution in N, N-dimethyl methyl
The ratio of amide is 0.3-0.5g:24mL；
In described step A, AOPAN nanofiber is prepared by following method:
A, polyacrylonitrile powder (PAN, weight average molecular weight is 79100) is dissolved in DMF (DMF),
Prepared mass percent is the solution of 10-12%, and solution is carried out high-voltage electrostatic spinning, prepares PAN nanofiber；Spinning technique
Parameter is set to: spinning speed 0.4-0.6mL/min, and spray webbing syringe needle (internal diameter 0.7mm, needle point polishes) receives plate with aluminium foil
Distance 15-17cm, spinning electrostatic pressure is 18-20kV, and the reception time is 22-26h；
B, by PAN nanofiber concentration be 0.5mmol/L, pH be 5.5-6.5, temperature be the oxammonium hydrochloride. of 68-70 DEG C
Solution soaks 120-150min, cleans 3-5 time with deionized water, be vacuum dried 120min at 40 DEG C, prepare AOPAN
Nanofiber；Described PAN nanofiber concentration in hydroxylamine hydrochloride solution is 10g/L.
The present invention, by the amidoximeization modification to Static Spinning PAN nanofiber, successfully prepares form stable, rich surface containing the most humorous
The AOPAN nanofiber of amidoxime active group, utilizes AOPAN nanofiber to carry out ATRP reaction as matrix first, prepares shape
State is stable, and porosity is high, and specific surface area is big, and the functional nano fiber of a large amount of ester group and free hydroxyl active group is contained on surface,
The fields such as this material can be applicable to macromole filtration, enzyme is fixed, adsorption of metal ions, have the most functional；Utilize non-sternly
(non-stringent) oxygen free condition of lattice, is converted into CuCl by the CuCl of trace2, without as traditional ATRP anti-
CuCl and CuCl should be added the most simultaneously2, simplify the catalyst system of reaction；With the high specific surface area of product as foundation,
In ATRP course of reaction, nanoscale AOPAN corpus fibrosum reveals the dynamic characteristic different from conventional AOPAN fiber, during reaction
Between shortened to 40-60min by the 6-8h of conventional fibre.
Accompanying drawing explanation
Fig. 1 prepares the process chart of functional AOPAN nanofiber preparation method.
The SEM figure of the functional AOPAN nanofiber of Fig. 2 example 1 preparation.
Detailed description of the invention
Embodiment 1:
A kind of functional AOPAN nanofiber, by AOPAN nanofiber surface grafted methacrylic acid hydroxyethyl ester (HEMA)
Molecular brush is constituted, and its structural representation formula is:
Wherein: n=30-50.
A kind of preparation method of functional AOPAN nanofiber, step includes:
Polyacrylonitrile powder (PAN, weight average molecular weight is 79100) is dissolved in DMF (DMF), prepares
Mass percent is the solution of 12%, and solution is carried out high-voltage electrostatic spinning；Spinning technology parameter is set to: spinning speed 0.4
ML/min, spray webbing syringe needle (internal diameter 0.7mm, needle point polishes) receives plate distance 17cm with aluminium foil, and it is 20kV that spinning electrostatic is pressed,
The reception time is 24h.By 1g PAN nanofiber 100mL concentration be 0.5mmol/L, pH be 6.0, temperature be 68
DEG C hydroxylamine hydrochloride solution in soak 150min, with deionized water clean 3 times, 40 DEG C be vacuum dried 120min, prepare
AOPAN nano fibrous membrane.
0.4g AOPAN nanofiber is put into equipped with the conical flask of 50mLTHF impregnates 10min, then in bottle, add 55 μ L
2-bromo-2-methyl-prop acylbromide (2-BIB) and 70 μ L triethylamines, place 4h, reaction a little in 35 DEG C of water-baths after shake
Respectively with THF washing 2 times, deionized water wash 2 times after end, it is vacuum dried 120min at 40 DEG C.By 0.4mL
1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl triethylene tetramines (HMTETA) are mixed in a boiling flask, by other one with the DMF of 24mL
Loading the HEMA of 24mL in boiling flask, so latter two boiling flask uses liquid nitrogen freezing 5 minutes respectively, is then placed on and has taken out
Defrosting 60min in the glove box of vacuum.This process of freezing and thawing is repeated twice.
In vacuum glove box, the CuCl of 0.08 gram is poured into above-mentioned through repeatedly freezing and thaw equipped with DMF, HMTETA
Boiling flask in, stir dissolution 60min, be then poured into above-mentioned another one through repeatedly freezing and thaw equipped with HEMA
Boiling flask in, slightly rock.The AOPAN nanofiber caused through 2-BIB is put into above-mentioned be mixed with HEMA, HMTETA,
In the boiling flask of DMF, CuCl, after rocking a little, it is allowed to react 40min.After reaction terminates, nanofiber is taken out,
With washes of absolute alcohol 3 times, taking-up is dried.
Embodiment 2
A kind of functional AOPAN nanofiber, by AOPAN nanofiber surface grafted methacrylic acid hydroxyethyl ester (HEMA)
Molecular brush is constituted, and its structural representation formula is:
Wherein: n=30-50.
A kind of preparation method of functional AOPAN nanofiber, step includes:
Polyacrylonitrile powder (PAN, weight average molecular weight is 79100) is dissolved in DMF (DMF), prepares
Mass percent is the solution of 10%, and solution is carried out high-voltage electrostatic spinning；Spinning technology parameter is set to: spinning speed 0.5
ML/min, spray webbing syringe needle (internal diameter 0.7mm, needle point polishes) receives plate distance 16cm with aluminium foil, and it is 18kV that spinning electrostatic is pressed,
The reception time is 24h.By 1g PAN nanofiber 100mL concentration be 0.5mmol/L, pH be 6.0, temperature be 70
DEG C hydroxylamine hydrochloride solution in soak 120min, with deionized water clean 3 times, 40 DEG C be vacuum dried 120min, prepare
AOPAN nano fibrous membrane.
0.4g AOPAN nanofiber is put into equipped with the conical flask of 50mLTHF impregnates 10min, then in bottle, add 60 μ L
2-bromo-2-methyl-prop acylbromide (2-BIB) and 70 μ L triethylamines, place 4h, reaction a little in 35 DEG C of water-baths after shake
Respectively with THF washing 2 times, deionized water wash 2 times after end, it is vacuum dried 120min at 40 DEG C.By 0.5mL
1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl triethylene tetramines (HMTETA) are mixed in a boiling flask, by other one with the DMF of 24mL
Loading the HEMA of 24mL in boiling flask, so latter two boiling flask uses liquid nitrogen freezing 5 minutes respectively, is then placed on and has taken out
Defrosting 60min in the glove box of vacuum.This process of freezing and thawing is repeated twice.
In vacuum glove box, the CuCl of 0.08 gram is poured into above-mentioned through repeatedly freezing and thaw equipped with DMF, HMTETA
Boiling flask in, stir dissolution 60min, be then poured into above-mentioned another one through repeatedly freezing and thaw equipped with HEMA
Boiling flask in, slightly rock.The AOPAN nanofiber caused through 2-BIB is put into above-mentioned be mixed with HEMA, HMTETA,
In the boiling flask of DMF, CuCl, after rocking a little, it is allowed to react 50min.After reaction terminates, nanofiber is taken out,
With washes of absolute alcohol 3 times, taking-up is dried.
Embodiment 3
A kind of functional AOPAN nanofiber, by AOPAN nanofiber surface grafted methacrylic acid hydroxyethyl ester (HEMA)
Molecular brush is constituted, and its structural representation formula is:
Wherein: n=30-50.
A kind of preparation method of functional AOPAN nanofiber, step includes:
Polyacrylonitrile powder (PAN, weight average molecular weight is 79100) is dissolved in DMF (DMF), prepares
Mass percent is the solution of 10%, and solution is carried out high-voltage electrostatic spinning；Spinning technology parameter is set to: spinning speed 0.5
ML/min, spray webbing syringe needle (internal diameter 0.7mm, needle point polishes) receives plate distance 16cm with aluminium foil, and it is 18kV that spinning electrostatic is pressed,
The reception time is 24h.By 1g PAN nanofiber 100mL concentration be 0.5mmol/L, pH be 6.0, temperature be 70
DEG C hydroxylamine hydrochloride solution in soak 120min, with deionized water clean 3 times, 40 DEG C be vacuum dried 120min, prepare
AOPAN nano fibrous membrane.
0.4g AOPAN nanofiber is put into equipped with the conical flask of 50mLTHF impregnates 10min, then in bottle, add 60 μ L
2-bromo-2-methyl-prop acylbromide (2-BIB) and 70 μ L triethylamines, place 4h, reaction a little in 35 DEG C of water-baths after shake
Respectively with THF washing 2 times, deionized water wash 2 times after end, it is vacuum dried 120min at 40 DEG C.By 0.5mL
1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl triethylene tetramines (HMTETA) are mixed in a boiling flask, by other one with the DMF of 24mL
Loading the HEMA of 24mL in boiling flask, so latter two boiling flask uses liquid nitrogen freezing 5 minutes respectively, is then placed on and has taken out
Defrosting 60min in the glove box of vacuum.This process of freezing and thawing is repeated twice.
In vacuum glove box, the CuCl of 0.1 gram is poured into above-mentioned through flat equipped with DMF, HMTETA that be repeatedly freezing and that thaw
In flask, stir dissolution 60min, be then poured into above-mentioned another one through repeatedly freezing and putting down equipped with HEMA of thawing
In end flask, slightly rock.The AOPAN nanofiber caused through 2-BIB is put into above-mentioned be mixed with HEMA, HMTETA, DMF,
In the boiling flask of CuCl, after rocking a little, it is allowed to react 60min.After reaction terminates, nanofiber is taken out, with anhydrous
Ethanol purge 3 times, taking-up is dried.
Functional AOPAN nanofiber embodiment 1-3 prepared uses DATAPHYSICS dynamic Contact angle measuring instrument
(DCAT11) carry out hydrophilicity test, use gold angstrom spectrum specific surface area and aperture tester (F-sorb2400) to carry out comparing table
Area, pore volume and opening size test, test result is shown in Tables 1 and 2.
As can be seen from Table 1, the functional AOPAN nanofiber that prepared by embodiment 1-3 and PAN nanofiber (advancing angle
(θA) 79.42, receding angle (θR) 64.87, contact angle hysteresis (Δ θ) 14.55；BET specific surface area (m2/g)20.89、
Pore volume (mL/g) 0.0419, average pore size (nm) 12.5) and AOPAN nanofiber (advancing angle (θA) 58.61, after
Move back angle (θR) 44.23, contact angle hysteresis (Δ θ) 14.38；BET specific surface area (m2/ g) 18.15, pore volume (mL/g)
0.0392, average pore size (nm) 10.8) compare, its hydrophilicity and specific surface area all improve a lot.
Dynamic contact angle (°) test result of functional AOPAN nanofiber prepared by table 1. embodiment 1-3
| Advancing angle (θA) | Receding angle (θR) | Contact angle hysteresis | |
| Embodiment 1 | 34.25 | 26.36 | 7.89 |
| Embodiment 2 | 31.84 | 25.12 | 6.72 |
| Embodiment 3 | 31.31 | 23.14 | 8.17 |
The BET specific surface area of functional AOPAN nanofiber, pore volume and opening size test result prepared by table 2. embodiment 1-3
| BET specific surface area (m2/g) | Pore volume (mL/g) | Average pore size (nm) | |
| Embodiment 1 | 24.15 | 0.0384 | 9.6 |
| Embodiment 2 | 25.91 | 0.0369 | 8.8 |
| Embodiment 3 | 22.82 | 0.0312 | 8.4 |
Functional AOPAN nanofiber embodiment 1-3 prepared is used for catalatic fixing, obtains high capacity rate and height
The immobilized enzyme of activity, (fixed amount Bradford method measures its specific activity, and specific activity is defined as every milligram of immobilization per minute
Zymolytic H2O2Micromole's number) and kinetic parameter (trying to achieve with Michaelis-Menten equation) be shown in Table 3.
Functional AOPAN nanometer fiber immobilization prepared by table 3. embodiment 1-3 crosses Rate activity and the kinetic parameter of enzyme
Claims (6)
1. a functional AOPAN nanofiber, by AOPAN nanofiber surface grafted methacrylic acid hydroxyethyl ester molecule
Brush is constituted, and its structural representation formula is:
Wherein: n=30-50.
2. a preparation method for functional AOPAN nanofiber, step includes:
A, AOPAN nanofiber is impregnated in oxolane more than 5min, be subsequently adding 2-bromo-2-methyl-prop acylbromide and
Triethylamine, 30-40 DEG C of heating in water bath 3-4h after mix homogeneously, uses oxolane respectively by reacted AOPAN nanofiber
Wash with water, vacuum drying, prepare the AOPAN nanofiber that free radical causes；
B into, CuCl is poured the 1,1,4,7,10,10-hexamethyl of freezing deoxygenation after mixing with the ratio of volume ratio 0.3-0.5:24
In triethylene tetramine and DMF mixture, stirring and evenly mixing, it is subsequently adding the methacrylic acid after freezing deoxygenation
Hydroxyethyl ester prepares mixed solution；
Described deoxidation method for will be equipped with 1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl triethylene tetramines and DMF mixture
Container and equipped with container more than the liquid nitrogen freezing 5min of methacrylate, then the container after freezing is being taken out
The glove box of vacuum thaws, repeated freezing and thawing process more than 2 times；
The AOPAN nanofiber that C, free radical step A prepared cause is put in the mixed solution that step B prepares, reaction
After 40-60min, nanofiber taking-up is clean with washes of absolute alcohol, dry prepared functional AOPAN nanofiber.
3. preparation method as claimed in claim 2, it is characterised in that: AOPAN nanofiber, the bromo-2-of 2-in described step A
Methyl-prop acylbromide and the triethylamine concentration in oxolane be respectively 0.3-0.5g/50mL, 55-65 μ L/50mL, 70
μL/50mL。
4. preparation method as claimed in claim 2, it is characterised in that: CuCl, N described in described step B, N-dimethyl
Methanamide, the ratio of methacrylate are 0.08-0.1g:24mL:24mL.
5. preparation method as claimed in claim 2, it is characterised in that: the free radical that step A described in described step C prepares
The ratio of the DMF in the mixed solution that the AOPAN nanofiber caused and step B prepare is 0.3-0.5g:
24mL。
6. preparation method as claimed in claim 2, it is characterised in that: under in described step A, AOPAN nanofiber passes through
Prepared by the method for stating:
A, being dissolved in DMF by polyacrylonitrile powder, prepared mass percent is the solution of 10-12%, by molten
Liquid carries out high-voltage electrostatic spinning, prepares PAN nanofiber；Spinning technology parameter is set to: spinning speed 0.4-0.6mL/min,
Spray webbing syringe needle and aluminium foil receive plate distance 15-17cm, and spinning electrostatic pressure is 18-20kV, and the reception time is 22-26h；
B, by PAN nanofiber concentration be 0.5mmol/L, pH be 5.5-6.5, temperature be the oxammonium hydrochloride. of 68-70 DEG C
Solution soaks 120-150min, cleans 3-5 time with deionized water, be vacuum dried 120min at 40 DEG C, prepare AOPAN
Nanofiber；Described PAN nanofiber concentration in hydroxylamine hydrochloride solution is 10g/L.
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| CN106544861B (en) * | 2016-10-12 | 2019-09-10 | 安徽工程大学 | A kind of preparation method and applications of functionality AOPAN-AA nano fibrous membrane |
| CN108660753A (en) * | 2018-05-04 | 2018-10-16 | 安徽工程大学 | A kind of preparation method of absorption heavy metal ion spun lacing viscose fiber non-woven cloth |
| CN115787284B (en) * | 2022-11-22 | 2024-04-19 | 核工业北京化工冶金研究院 | Metal ion adsorption material and preparation method and application thereof |
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| CN1207173A (en) * | 1995-10-30 | 1999-02-03 | 株式会社京都第一科学 | Method of measurement of material and testpiece |
| CN101899132A (en) * | 2010-07-26 | 2010-12-01 | 鲁东大学 | Preparation method of polyacrylonitrile adsorbing materials |
| CN102102097A (en) * | 2010-12-10 | 2011-06-22 | 江南大学 | Catalase immobilization method on basis of using amidoxime PAN nanofibrous membrane as carrier |
| WO2012101245A1 (en) * | 2011-01-28 | 2012-08-02 | Basf Se | Polymerizable composition comprising an oxime sulfonate as thermal curing agent |
| CN103037913A (en) * | 2010-06-09 | 2013-04-10 | 森普鲁斯生物科学公司 | Non-fouling, anti-microbial, anti-thrombogenic graft-from compositions |
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|---|---|---|---|---|
| CN1207173A (en) * | 1995-10-30 | 1999-02-03 | 株式会社京都第一科学 | Method of measurement of material and testpiece |
| CN103037913A (en) * | 2010-06-09 | 2013-04-10 | 森普鲁斯生物科学公司 | Non-fouling, anti-microbial, anti-thrombogenic graft-from compositions |
| CN101899132A (en) * | 2010-07-26 | 2010-12-01 | 鲁东大学 | Preparation method of polyacrylonitrile adsorbing materials |
| CN102102097A (en) * | 2010-12-10 | 2011-06-22 | 江南大学 | Catalase immobilization method on basis of using amidoxime PAN nanofibrous membrane as carrier |
| WO2012101245A1 (en) * | 2011-01-28 | 2012-08-02 | Basf Se | Polymerizable composition comprising an oxime sulfonate as thermal curing agent |
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