CN103966851A - Functional AOPAN nano-fiber and preparation method thereof - Google Patents
Functional AOPAN nano-fiber and preparation method thereof Download PDFInfo
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Abstract
The invention provides a functional AOPAN nano-fiber and a preparation method thereof. a hydroxyethyl methacrylate (HEMA) molecular brush is grafted on the surface of the AOPAN nano-fiber by virtue of an atom radical polymerization technology, and the prepared functional nano-fiber is stable in form and high in porosity, has large specific surface area and contains a large number of active groups on surface; moreover, by virtue of the preparation method, a reaction catalytic system is simplified and the reaction time is short.
Description
Technical field
The present invention relates to nano material preparing technical field, be specifically related to a kind of functional AOPAN nanofiber and preparation method thereof.
Background technology
The high polymer that utilization contains functional groups is matrix, and by MOLECULE DESIGN, the synthetic functional high molecule material with specific chemical constitution is the research emphasis of material science always.Atom transfer radical polymerization (ATRP) is utilized transition metal ions and is formed catalyst system and catalyzing to electronics part, by the initiation of free radical, specific macromolecular material is prepared in functional monomer polymerization, is a kind of reaction condition gentleness, operates relatively easy novel synthetic technology.
Utilize ATRP technology grafting HEMA molecular brush to need matrix surface to there is hydroxyl isoreactivity group as priming site, current this type of modification is all that cellulose fibre, paper etc. using conventional yardstick is as matrix, this type of matrix specific area is little, can provide the avtive spot of initiation and grafting few.Nanofiber has very large specific area, but the nanofiber preparation technology of cellulose base is still immature; The polyvinyl alcohol (PVA) of rich surface hydroxyl, although nanofiber is easily prepared, and has larger specific area, and this matrix is in process of grafting, and morphosis is unstable, loses even nanofiber form completely.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of functional AOPAN nanofiber and preparation method thereof, the present invention utilizes atom radical polymerization technique grafting methacrylic acid hydroxyethyl ester (HEMA) molecular brush on AOPAN nanofiber surface, the functional nano fibre morphology making is stable, porosity is high, specific area is large, and a large amount of active groups are contained on surface; Preparation method has simplified the catalyst system and catalyzing of reaction, and the reaction time is short.
The technical solution used in the present invention is:
A kind of functional AOPAN nanofiber, is made up of AOPAN nanofiber surface grafting methacrylic acid hydroxyethyl ester (HEMA) molecular brush, and its structural representation formula is:
Wherein: n=30-50.
A preparation method for functional AOPAN nanofiber, step comprises:
A, AOPAN nanofiber is flooded more than 5min in oxolane (THF), then add the bromo-2-methyl-prop of 2-acylbromide (2-BIB) and triethylamine, mix rear 30-40 DEG C of heating water bath 3-4h, reacted AOPAN nanofiber is used respectively to THF and water washing, vacuumize, makes the AOPAN nanofiber that free radical causes; Described AOPAN nanofiber, the bromo-2-methyl-prop of 2-acylbromide (2-BIB) and the concentration of triethylamine in oxolane are respectively 0.3-0.5g/50mL, 55-65 μ L/50mL, 70 μ L/50mL.
B, by CuCl pour into mix with the ratio of volume ratio 0.3-0.5:24 after freezing deoxygenation 1,1,4,7,10,10-hexamethyl triethylene tetramine (HMTETA) and N, in dinethylformamide (DMF) mixture, stir and evenly mix, then add the methacrylic acid hydroxyethyl ester (HEMA) after freezing deoxygenation to make mixed solution, the ratio of described CuCl, DMF, methacrylic acid hydroxyethyl ester is 0.08-0.1g:24mL:24mL;
Described deoxidation method will be for will be equipped with 1,1,4,7, more than the container of 10,10-hexamethyl triethylene tetramine (HMTETA) and DMF (DMF) mixture and container liquid nitrogen frozen 5min that methacrylic acid hydroxyethyl ester is housed, then the container after freezing is thawed in the glove box vacuumizing, repeated freezing and course of defrosting are more than 2 times.
The AOPAN nanofiber that C, the free radical that steps A is made cause is put into the mixed solution that step B makes, and after reaction 40-60min, nanofiber taking-up is cleaned up with absolute ethyl alcohol, dries and makes functional AOPAN nanofiber; The ratio of the DMF in the mixed solution that the AOPAN nanofiber that the free radical that described steps A makes causes and step B make is 0.3-0.5g:24mL;
In described steps A, AOPAN nanofiber is prepared by following method:
A, polyacrylonitrile powder (PAN, weight average molecular weight is 79100) is dissolved in DMF (DMF), makes the solution that mass percent is 10-12%, solution is carried out to high-voltage electrostatic spinning, make PAN nanofiber; Spinning technology parameter is set to: spinning speed 0.4-0.6mL/min, and spray silk syringe needle (internal diameter 0.7mm, needle point polishes) is with aluminium foil dash receiver apart from 15-17cm, and spinning electrostatic pressure is 18-20kV, and time of reception is 22-26h;
B, be that 0.5mmol/L, pH are that 5.5-6.5, temperature are to soak 120-150min in the hydroxylamine hydrochloride solution of 68-70 DEG C by PAN nanofiber in concentration, by washed with de-ionized water 3-5 time, at 40 DEG C of vacuumize 120min, make AOPAN nanofiber; The concentration of described PAN nanofiber in hydroxylamine hydrochloride solution is 10g/L.
The present invention is by the amidoxime modification to Static Spinning PAN nanofiber, successfully make form stable, the rich surface AOPAN nanofiber containing a large amount of humorous amidoxime active groups, utilize first AOPAN nanofiber to carry out ATRP reaction as matrix, make form stable, porosity is high, and specific area is large, the functional nano fiber that a large amount of ester groups and free hydroxyl active group are contained in surface, this material can be applicable to the fields such as large molecular filtration, enzyme are fixed, adsorption of metal ions, has functional significantly; Utilize non-strict (non-stringent) oxygen free condition, micro-CuCl is converted into CuCl
2, and do not need to add CuCl and CuCl as traditional ATRP reaction simultaneously
2, simplify the catalyst system reacting; Taking 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, and the reaction time shortens to 40-60min by the 6-8h of conventional fibre.
Brief description of the drawings
Fig. 1 prepares functional AOPAN nanofiber preparation method's process chart.
The SEM figure of functional AOPAN nanofiber prepared by Fig. 2 example 1.
Detailed description of the invention
Embodiment 1:
A kind of functional AOPAN nanofiber, is made up of AOPAN nanofiber surface grafting methacrylic acid hydroxyethyl ester (HEMA) molecular brush, and its structural representation formula is:
Wherein: n=30-50.
A preparation method for functional AOPAN nanofiber, step comprises:
Polyacrylonitrile powder (PAN, weight average molecular weight is 79100) is dissolved in DMF (DMF), makes mass percent and be 12% solution, solution is carried out to high-voltage electrostatic spinning; Spinning technology parameter is set to: spinning speed 0.4mL/min, and spray silk syringe needle (internal diameter 0.7mm, needle point polishes) is with aluminium foil dash receiver apart from 17cm, and spinning electrostatic pressure is 20kV, and time of reception is 24h.By 1g PAN nanofiber be in 100mL concentration that 0.5mmol/L, pH are 6.0, temperature is to soak 150min in the hydroxylamine hydrochloride solution of 68 DEG C, by washed with de-ionized water 3 times, at 40 DEG C of vacuumize 120min, makes AOPAN nano fibrous membrane.
0.4g AOPAN nanofiber is put into the conical flask that 50mLTHF is housed and flood 10min, in bottle, add 55 μ L2-bromo-2-methyl-prop acylbromide (2-BIB) and 70 μ L triethylamines again, after shake, in 35 DEG C of water-baths, place 4h a little, reaction finishes rear respectively with THF washing 2 times, deionized water washing 2 times, at 40 DEG C of vacuumize 120min.By 0.4mL1,1,4,7,10,10-hexamethyl triethylene tetramine (HMTETA) is mixed in a boiling flask with the DMF of 24mL, will in an other boiling flask, pack the HEMA of 24mL into, so latter two boiling flask is used respectively liquid nitrogen frozen 5 minutes, is then placed on the 60min that thaws in the glove box having vacuumized.This freezing and course of defrosting repeats 2 times again.
In vacuum glove box, the CuCl of 0.08 gram is poured into above-mentioned through in the freezing and boiling flask that DMF, HMTETA are housed that thaws repeatedly, stir dissolution 60min, be then poured into above-mentioned another one and be equipped with in the boiling flask of HEMA with thawing through repeatedly freezing, slightly rock.The AOPAN nanofiber causing through 2-BIB is put into the boiling flask of the above-mentioned HEMA of being mixed with, HMTETA, DMF, CuCl, after rocking a little, allowed it react 40min.After reaction finishes, nanofiber is taken out, with absolute ethyl alcohol cleaning 3 times, taking-up is dried.
Embodiment 2
A kind of functional AOPAN nanofiber, is made up of AOPAN nanofiber surface grafting methacrylic acid hydroxyethyl ester (HEMA) molecular brush, and its structural representation formula is:
Wherein: n=30-50.
A preparation method for functional AOPAN nanofiber, step comprises:
Polyacrylonitrile powder (PAN, weight average molecular weight is 79100) is dissolved in DMF (DMF), makes mass percent and be 10% solution, solution is carried out to high-voltage electrostatic spinning; Spinning technology parameter is set to: spinning speed 0.5mL/min, and spray silk syringe needle (internal diameter 0.7mm, needle point polishes) is with aluminium foil dash receiver apart from 16cm, and spinning electrostatic pressure is 18kV, and time of reception is 24h.By 1g PAN nanofiber be in 100mL concentration that 0.5mmol/L, pH are 6.0, temperature is to soak 120min in the hydroxylamine hydrochloride solution of 70 DEG C, by washed with de-ionized water 3 times, at 40 DEG C of vacuumize 120min, makes AOPAN nano fibrous membrane.
0.4g AOPAN nanofiber is put into the conical flask that 50mLTHF is housed and flood 10min, in bottle, add 60 μ L2-bromo-2-methyl-prop acylbromide (2-BIB) and 70 μ L triethylamines again, after shake, in 35 DEG C of water-baths, place 4h a little, reaction finishes rear respectively with THF washing 2 times, deionized water washing 2 times, at 40 DEG C of vacuumize 120min.By 0.5mL1,1,4,7,10,10-hexamethyl triethylene tetramine (HMTETA) is mixed in a boiling flask with the DMF of 24mL, will in an other boiling flask, pack the HEMA of 24mL into, so latter two boiling flask is used respectively liquid nitrogen frozen 5 minutes, is then placed on the 60min that thaws in the glove box having vacuumized.This freezing and course of defrosting repeats 2 times again.
In vacuum glove box, the CuCl of 0.08 gram is poured into above-mentioned through in the freezing and boiling flask that DMF, HMTETA are housed that thaws repeatedly, stir dissolution 60min, be then poured into above-mentioned another one and be equipped with in the boiling flask of HEMA with thawing through repeatedly freezing, slightly rock.The AOPAN nanofiber causing through 2-BIB is put into the boiling flask of the above-mentioned HEMA of being mixed with, HMTETA, DMF, CuCl, after rocking a little, allowed it react 50min.After reaction finishes, nanofiber is taken out, with absolute ethyl alcohol cleaning 3 times, taking-up is dried.
Embodiment 3
A kind of functional AOPAN nanofiber, is made up of AOPAN nanofiber surface grafting methacrylic acid hydroxyethyl ester (HEMA) molecular brush, and its structural representation formula is:
Wherein: n=30-50.
A preparation method for functional AOPAN nanofiber, step comprises:
Polyacrylonitrile powder (PAN, weight average molecular weight is 79100) is dissolved in DMF (DMF), makes mass percent and be 10% solution, solution is carried out to high-voltage electrostatic spinning; Spinning technology parameter is set to: spinning speed 0.5mL/min, and spray silk syringe needle (internal diameter 0.7mm, needle point polishes) is with aluminium foil dash receiver apart from 16cm, and spinning electrostatic pressure is 18kV, and time of reception is 24h.By 1g PAN nanofiber be in 100mL concentration that 0.5mmol/L, pH are 6.0, temperature is to soak 120min in the hydroxylamine hydrochloride solution of 70 DEG C, by washed with de-ionized water 3 times, at 40 DEG C of vacuumize 120min, makes AOPAN nano fibrous membrane.
0.4g AOPAN nanofiber is put into the conical flask that 50mLTHF is housed and flood 10min, in bottle, add 60 μ L2-bromo-2-methyl-prop acylbromide (2-BIB) and 70 μ L triethylamines again, after shake, in 35 DEG C of water-baths, place 4h a little, reaction finishes rear respectively with THF washing 2 times, deionized water washing 2 times, at 40 DEG C of vacuumize 120min.By 0.5mL1,1,4,7,10,10-hexamethyl triethylene tetramine (HMTETA) is mixed in a boiling flask with the DMF of 24mL, will in an other boiling flask, pack the HEMA of 24mL into, so latter two boiling flask is used respectively liquid nitrogen frozen 5 minutes, is then placed on the 60min that thaws in the glove box having vacuumized.This freezing and course of defrosting repeats 2 times again.
In vacuum glove box, the CuCl of 0.1 gram is poured into above-mentioned through in the freezing and boiling flask that DMF, HMTETA are housed that thaws repeatedly, stir dissolution 60min, be then poured into above-mentioned another one and be equipped with in the boiling flask of HEMA with thawing through repeatedly freezing, slightly rock.The AOPAN nanofiber causing through 2-BIB is put into the boiling flask of the above-mentioned HEMA of being mixed with, HMTETA, DMF, CuCl, after rocking a little, allowed it react 60min.After reaction finishes, nanofiber is taken out, with absolute ethyl alcohol cleaning 3 times, taking-up is dried.
Functional AOPAN nanofiber prepared by embodiment 1-3 uses DATAPHYSICS dynamic Contact angle measuring instrument (DCAT11) to carry out hydrophilicity test, use golden dust spectrum specific area and aperture tester (F-sorb2400) to carry out specific area, pore volume and aperture test, test result is in table 1 and table 2.
As can be seen from Table 1, functional AOPAN nanofiber and the PAN nanofiber (advancing angle (θ that prepared by embodiment 1-3
a) 79.42, receding angle (θ
r) 64.87, contact angle hysteresis (Δ θ) 14.55; BET specific area (m
2/ g) 20.89, pore volume (mL/g) 0.0419, average pore size (nm) 12.5) and AOPAN nanofiber (advancing angle (θ
a) 58.61, receding angle (θ
r) 44.23, contact angle hysteresis (Δ θ) 14.38; BET specific area (m
2/ g) 18.15, pore volume (mL/g) 0.0392, average pore size (nm) 10.8) relatively, its hydrophilicity and specific area all improve a lot.
The dynamic contact angle of functional AOPAN nanofiber prepared by table 1. embodiment 1-3 (°) test result
| Advancing angle (θ A) | Receding angle (θ R) | 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 |
BET specific area, pore volume and the aperture test result of functional AOPAN nanofiber prepared by table 2. embodiment 1-3
| BET specific area (m 2/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 prepared by embodiment 1-3 is for catalatic fixing, obtain high capacity rate and highly active immobilised enzymes, its specific activity (measure by Bradford method, and specific activity is defined as the zymolytic H of every milligram of immobilization per minute by fixed amount
2o
2micromole's number) and kinetic parameter (trying to achieve with Michaelis-Menten equation) in table 3.
Functional AOPAN nanometer fiber immobilization prepared by table 3. embodiment 1-3 is crossed ratio vigor and the kinetic parameter of enzyme
Claims (6)
1. a functional AOPAN nanofiber, is made up of AOPAN nanofiber surface grafting methacrylic acid hydroxyethyl ester molecular brush, and its structural representation formula is:
Wherein: n=30-50.
2. a preparation method for functional AOPAN nanofiber, step comprises:
A, AOPAN nanofiber is flooded to 5min in oxolane more than, then add 2-bromo-2-methyl-prop acylbromide and triethylamine, mix rear 30-40 DEG C of heating water bath 3-4h, reacted AOPAN nanofiber is used respectively to oxolane and water washing, vacuumize, makes the AOPAN nanofiber that free radical causes;
B, by CuCl pour into mix with the ratio of volume ratio 0.3-0.5:24 after freezing deoxygenation 1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl triethylene tetramine and N, in dinethylformamide mixture, stir and evenly mix, then add the methacrylic acid hydroxyethyl ester after freezing deoxygenation to make mixed solution;
Described deoxidation method will be for will be equipped with 1,1,4,7, more than the container of 10,10-hexamethyl triethylene tetramine and DMF mixture and container liquid nitrogen frozen 5min that methacrylic acid hydroxyethyl ester is housed, then the container after freezing is thawed in the glove box vacuumizing, repeated freezing and course of defrosting are more than 2 times.
The AOPAN nanofiber that C, the free radical that steps A is made cause is put into the mixed solution that step B makes, and after reaction 40-60min, nanofiber taking-up is cleaned up with absolute ethyl alcohol, dries and makes functional AOPAN nanofiber.
3. preparation method as claimed in claim 2, is characterized in that: in described steps A, AOPAN nanofiber, 2-bromo-2-methyl-prop acylbromide and the concentration of triethylamine in oxolane are respectively 0.3-0.5g/50mL, 55-65 μ L/50mL, 70 μ L/50mL.
4. preparation method as claimed in claim 2, is characterized in that: the ratio of CuCl described in described step B, DMF, methacrylic acid hydroxyethyl ester is 0.08-0.1g:24mL:24mL.
5. preparation method as claimed in claim 2, is characterized in that: the ratio of the DMF in the mixed solution that the AOPAN nanofiber that the free radical that described in described step C, steps A makes causes and step B make is 0.3-0.5g:24mL.
6. preparation method as claimed in claim 2, is characterized in that: in described steps A, AOPAN nanofiber is prepared by following method:
A, polyacrylonitrile powder is dissolved in DMF, makes the solution that mass percent is 10-12%, solution is carried out to high-voltage electrostatic spinning, make PAN nanofiber; Spinning technology parameter is set to: spinning speed 0.4-0.6mL/min, and spray silk syringe needle and aluminium foil dash receiver are apart from 15-17cm, and spinning electrostatic pressure is 18-20kV, and time of reception is 22-26h;
B, be that 0.5mmol/L, pH are that 5.5-6.5, temperature are to soak 120-150min in the hydroxylamine hydrochloride solution of 68-70 DEG C by PAN nanofiber in concentration, by washed with de-ionized water 3-5 time, at 40 DEG C of vacuumize 120min, make AOPAN nanofiber; The concentration of described PAN nanofiber in hydroxylamine hydrochloride solution is 10g/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106544861A (en) * | 2016-10-12 | 2017-03-29 | 安徽工程大学 | A kind of preparation method and applications of feature AOPAN AA nano fibrous membranes |
| 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 |
| CN115787284A (en) * | 2022-11-22 | 2023-03-14 | 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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| 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 |
| CN115787284A (en) * | 2022-11-22 | 2023-03-14 | 核工业北京化工冶金研究院 | Metal ion adsorption material and preparation method and application thereof |
| 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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