CN104845006A - Magnetic acrylamide hydrogel and preparation method thereof - Google Patents

Magnetic acrylamide hydrogel and preparation method thereof Download PDF

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Publication number
CN104845006A
CN104845006A CN201510236288.7A CN201510236288A CN104845006A CN 104845006 A CN104845006 A CN 104845006A CN 201510236288 A CN201510236288 A CN 201510236288A CN 104845006 A CN104845006 A CN 104845006A
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hydrogel
magnetic
preparation
nano
acrylic amide
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鲁希华
马天泽
赵迪
李雪婷
刘维伊
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Donghua University
National Dong Hwa University
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Donghua University
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Abstract

The invention relates to a magnetic acrylamide hydrogel and a preparation method thereof. The hydrogel is obtained by coating poly(tert-butyl acrylamide-co-crylic acid)P(NtBAM-co-AAc) with Fe3O4 particles. The preparation method comprises the steps of (1) dissolving monomer N- tert-butyl acrylamide, monomer crylic acid, emulsifier and a crosslinking agent into deionized water, stirring at 15-40 DEG C in nitrogen atmosphere, then rising temperature to 60-90 DEG C, preserving the temperature, then adding an initiator, reacting for 0.5-10 hours, and dialyzing to obtain copoly nano-hydrogel; (2) adjusting pH of the copoly nano-hydrogel, adding FeSO4.7H2O, stirring, dialyzing, adding NaNO2 and NH3.H2O, and dialyzing after reaction to obtain the hydrogel. The magnetic acrylamide hydrogel has better size controllability, monodispersity and excellent magnetism compared with traditional Fe3O4-coated particle compound. The preparation method is simple in process and environment-friendly.

Description

A kind of magnetic acrylic amide hydrogel and preparation method thereof
Technical field
The invention belongs to hydrogel and preparation field thereof, particularly a kind of magnetic acrylic amide hydrogel and preparation method thereof.
Background technology
Magnetic hydrogel has the two-fold advantage of aquogel polymer and inorganic particle, thus in field extensive application such as biomedicine, nonlinear optical material, Materials science, environmental protection, biotechnology, electrochemical indicating meter, molecular device, electromagnetic shielding, microwave absorbing.Especially magnetic particle has been studied and has been applied to magnetic thermotherapy, drug conveying, nuclear magnetic resonance etc. in biomedicine, but due to magnetic particle particle diameter too little, surface energy is high, easily assembles, and common magnetic particle Fe 3o 4surfaces hydrophobic, therefore can adopt hydrophilic hydrogel to be coated with and be applied in body.Poly N-isopropyl acrylamide (PNIPA) is most typical, also be the widest hydrogel of investigation and application, its Volume-phase transition temperature (VPTT) is 32 DEG C, comparatively close to body temperature, this makes it be widely used in the Co ntrolled release of enzyme immobilizatio, medicine, the field such as bio-medical material and bio-molecular separation purification.
N tert butyl acrylamide (NtBAM) and NIPA similar, can generate the polymkeric substance of temperature-responsive, namely have temperature sensitivity.Compared with NIPA, the amide group end of NtBAM is the tertiary butyl, and NIPA is sec.-propyl, both compare mutually, and biological property is close, but NtBAM ending volume is larger, when forming nano-hydrogel with NIPA same case, NtBAM formed nano-hydrogel particle diameter less, be easy to control.Because NtBAM hydrogel particle diameter is less, when being applied to inside of human body, be not easy to assemble blocking kapillary or tissue, therefore have biocompatibility relatively preferably, be more suitable for being applied in life science.Existing Many researchers is devoted to the research of poly-N tert butyl acrylamide (NtBAM) hydrogel at present.The people such as Atsushi Narumi as the U.S. synthesizes PNtBAM (Atsushi Narumi, Yudai Kimura, SeigouKawaguchi.Colloid Polym Sci.2012,290,379-384) in water.More investigator is exploring character and the purposes of NtBAM composite aquogel or copolymer hydrogel, as: the people such as M.Teresa Garay synthesize PNtBAM and PAAc IPN hydrogel, and discuss impact (the M.Teresa Garay of solvent on it, Leire Ruiz, J.Ram ó n Mar í n, J.Manuel Laza, MatildeRodriguez, Luis M.Le ó n.Colloid Polym Sci.2010,288,1593-1599); the people such as Demirel prepare P (NtBAM-co-AAm/MA) marking ionic copolymerization hydrogel for bovine serum albumin, this hydrogel to temperature and pH have Dual Sensitive ( demire, eylem Turan, Tuncer macromol.Biosci..2005,5,1032-1037).Also there is investigator that NtBAM is applied to synthesizing magnetic hydrogel, as the people such as Tuncer Caykara utilize FeCl 36H 2o and FeSO 47H 2o coprecipitation method synthesizes Fe at the P prepared (NtBAM-co-AAm) hydrogel internal in-situ 3o 4particle (Tuncer Caykara, serkan Demirci.Journal of Applied PolymerScience DOI.2009,112,800-804).
At present, use P (NtBAM-co-AAc) as the coating layer material of magnetic hydrogel, and only use FeSO 47H 2o is in-situ oxidation reduction synthesis Fe in the hydrogel taking NtBAM as raw material 3o 4the report that the method for particle there is not yet.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of magnetic acrylic amide hydrogel and preparation method thereof, and this magnetic hydrogel is than traditional coated Fe 3o 4particle composite has better dimensional controllability, monodispersity, because single hydrogel inside can comprise multiple Fe 3o 4crystal particles, magnetic is also more excellent; Preparation method's technique is simple, environmental protection.
A kind of magnetic acrylic amide hydrogel of the present invention, described hydrogel is by gathering (N-tertiary butyl acrylamide-co-vinylformic acid) P (NtBAM-co-AAc) coated Fe 3o 4particle obtains.
Described P (NtBAM-co-AAc) comprises repeating unit A and repeating unit B; Wherein the structural formula of A is b structural formula is
The preparation method of a kind of magnetic acrylic amide hydrogel of the present invention, comprising:
(1) monomer N tert butyl acrylamide, monomeric acrylic, emulsifying agent and linking agent are dissolved in deionized water, under nitrogen atmosphere, under 15-40 DEG C of condition, stir, be warming up to 60-90 DEG C, insulation, then initiator is added, continue reaction 0.5-10h, dialysis, obtains compolymer/nano hydrogel; Wherein, monomeric acrylic accounts for the 5%-50% of monomer integral molar quantity;
(2) above-mentioned compolymer/nano hydrogel is adjusted pH to 5.5 ± 1.5, add FeSO 47H 2o, at N 24-24h is stirred, dialysis 0.5-5h, N under atmosphere 2stir 2 ~ 4h under atmosphere, add NaNO 2solution and NH 3h 2o, reaction 2-10h, namely dialysis treatment obtains magnetic Nano hydrogel; Wherein, FeSO 47H 2the add-on of O is the 0.01%-10% of compolymer/nano hydrogel quality summation.
In described step (1), the total amount of monomer N tert butyl acrylamide and monomeric acrylic is 0.5 ~ 5g.
12. emulsifying agent is sodium lauryl sulphate in described step (1), add-on is the 0.1%-20%. of monomer mass summation
In described step (1), linking agent is N, N '-methylene-bisacrylamide, add-on is the 1%-30% of monomer mass summation.
In described step (1), initiator is ammonium persulphate, and add-on is the 0.1%-10% of monomer mass summation.
In described step (1), churning time is 30-120min.
In described step (1), soaking time is 30-60min.
NaNO in described step (2) 2add-on be the 0.001%-1% of compolymer/nano hydrogel quality summation; The add-on of ammoniacal liquor is the 1%-25% of compolymer/nano hydrogel quality summation.
Dialyse as adopting deionized water to soak 4-8 days in described step (1) and step (2), change twice water every day, the molecular weight cut-off of dialysis tubing used is 8000-14000.
NaOH adjust ph is used in described step (2).
The massfraction of the ammoniacal liquor in described step (2) is 28%.
The present invention is to prepare the monomer N tert butyl acrylamide (NtBAM) of poly-(N tert butyl acrylamide) (PNtBAM) of temperature-sensitive macromolecular for monomer, with hydrophilic vinylformic acid (AAc) for function monomer, adopt the method for letex polymerization, by introduce hydrophilic body monomer content number control the particle diameter of hydrogel.After this Fe is synthesized by oxidation in situ in hydrogel inside 3o 4particle, makes hydrogel have magnetic, prepares a kind of magnetic acrylic amide nano-hydrogel.
The present invention utilizes hydrophilic monomer AA c ionizable in aqueous, and the feature attracting according to zwitterion adsorbs iron ion with it, therefore AAc is used to be incorporated in the polymkeric substance of temperature sensitive monomer NtBAM as functional monomer, prepared NtBAM/AAc copolymer nano hydrogel P (NtBAM-co-AAc) containing high-hydrophilic monomer by letex polymerization, this hydrogel has temperature, pH double-response susceptibility.After this Fe is synthesized by oxidation in situ in hydrogel inside 3o 4particle, prepares P (NtBAM-co-AAc)/Fe 3o 4this magnetic acrylic amide hydrogel, establishes the preparation method of this magnetic Nano hydrogel.
Bring out high-content hydrophilic monomer NtBAM and AAc when initiator and the low consumption of linking agent and copolymerization occurs, synthesize a kind of nanometer copolymer hydrogel, and introduce iron ion in nano-hydrogel P (NtBAM-co-AAc) inside, make iron ion generation in-situ oxidation generate Fe by the pH changing system 3o 4particle, thus successfully prepare magnetic Nano hydrogel P (NtBAM-co-AAc)/Fe 3o 4.Adding of hydrophilic monomer AA c can lure that more iron ion enters gel inside into, thus makes Fe 3o 4particle is more wrapped by, and improves the magnetic of single hydrogel, and can change the magnetic responsiveness of hydrogel, widens materials application scope.
Two kinds of monomers are synthesized a kind of magnetic acrylic amide nano-hydrogel P (NtBAM-co-AAc) by letex polymerization by the present invention, this material has very large application prospect in biomedicine, such as can be used as contrast medium when nuclear magnetic resonance, improve magnetic signal during nucleus magnetic resonance, and the sharpness of imaging can be improved, improve the contrast gradient of image between pathological tissues and healthy tissues.This material can not only overcome superparamagnetism Fe 3o 4particle diameter is too small, surface energy is high, be easy to the shortcoming of gathering, can also change its surface hydrophobicity, improve biocompatibility.
beneficial effect
(1) simple, the environmental protection of the method technique that adopts of the present invention, prepares the magnetic hydrogel of gained than traditional coated Fe 3o 4particle composite has better dimensional controllability, monodispersity, because single hydrogel inside can comprise multiple Fe 3o 4crystal particles, magnetic is also more excellent;
(2) two kinds of monomers are synthesized a kind of magnetic acrylic amide nano-hydrogel P (NtBAM-co-AAc) by letex polymerization by the present invention, and this material can not only overcome superparamagnetism Fe 3o 4particle diameter is too small, surface energy is high, be easy to the shortcoming of gathering, and can also change its surface hydrophobicity, improve biocompatibility, this material has very large application prospect in biomedicine.
Accompanying drawing explanation
Fig. 1 is P (NtBAM-co-AAc) or P (the NtBAM-co-AAc)/Fe that numbering is respectively a ~ d 3o 4pictorial diagram; Wherein, a is the pictorial diagram of P (NtBAM-co-AAc) in embodiment 1, and b is the pictorial diagram of P (NtBAM-co-AAc) in embodiment 2, and c is P (NtBAM-co-AAc)/Fe in embodiment 3 3o 4pictorial diagram, d is P (NtBAM-co-AAc)/Fe in embodiment 4 3o 4pictorial diagram;
Fig. 2 is the dispersed test result of the sample a ~ d in embodiment 1-4;
Fig. 3 is the grain size distribution of the sample a ~ d in embodiment 1-4;
Fig. 4 is the FT-IR figure of d in a and embodiment 4 in embodiment 1;
Fig. 5 is the XRD spectra of d in c and embodiment 4 in embodiment 3;
Fig. 6 is the histogram of the Fe content of d in c and embodiment 4 in embodiment 3.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) get 0.7282g NIPA NtBAM, 0.0467g vinylformic acid AAc, 0.0212g N, N '-methylene-bisacrylamide and 0.0402g sodium lauryl sulphate are dissolved in 90g deionized water, and blast N under room temperature 2deoxygenation, magnetic agitation 120min;
(2) temperature of reaction rises to 60 DEG C, at N 2the above-mentioned solution 40min of the lower insulation of protection;
(3) then preparing mass concentration is the ammonium persulfate solution of 0.6%, gets 9.9987g and adds in above-mentioned solution, keeps N 2atmosphere, continues reaction 3h;
(4) then gained reactant is soaked in deionized water and dialyses 5 days, every day changes intermediate water, removes ionogen in residual reaction raw materials and reaction system, dialysis tubing molecular weight cut-off used is 8000 ~ 14000, obtain the copolymer hydrogel of NtBAM and AAc, be numbered a, as shown in Figure 1.
Embodiment 2
(1) get 0.7259g NIPA NtBAM, 0.2740g vinylformic acid AAc, 0.0302g N, N '-methylene-bisacrylamide and 0.0205g sodium lauryl sulphate are dissolved in 90g deionized water, and blast N under room temperature 2deoxygenation, magnetic agitation 120min;
(2) temperature of reaction rises to 60 DEG C, at N 2the above-mentioned solution 40min of the lower insulation of protection;
(3) then preparing mass concentration is the ammonium persulfate solution of 0.6%, gets 10.0087g and adds in above-mentioned solution, keeps N 2atmosphere, continues reaction 3h;
(4) then gained reactant is soaked in deionized water and dialyses 5 days, every day changes intermediate water, removes ionogen in residual reaction raw materials and reaction system, dialysis tubing molecular weight cut-off used is 8000 ~ 14000, obtain the copolymer hydrogel of NtBAM and AAc, be numbered b, as shown in Figure 1.
Embodiment 3
(1) product 50mL in Example 1, uses NaOH to regulate pH to 6.42, with the FeSO of 0.1391g 47H 2o mixes, at room temperature, N 2stir a night in atmosphere, after this use above-mentioned dialysis tubing dialysis 2h;
(2) continue at room temperature, N 2after stirring 2h in atmosphere, add 0.054gNaNO 2;
(3) keep stirring 10min, use syringe to add 5mL ammoniacal liquor, continue reaction 3h;
(4) gained reactant soaks and dialyses 3 days in deionized water, changes twice water every day, uses above-mentioned dialysis tubing.Obtain the magnetic hydrogel of fabricated in situ, be numbered c, as shown in Figure 1.
Embodiment 4
(1) product 50mL in Example 1, uses NaOH to regulate pH to 6.27, with the FeSO of 0.0694g 47H 2o mixes, at room temperature, N 2stir a night in atmosphere, after this use above-mentioned dialysis tubing dialysis 2h;
(2) continue at room temperature, N 2after stirring 2h in atmosphere, add 0.052gNaNO 2;
(3) keep stirring 10min, use syringe to add 5mL ammoniacal liquor, continue reaction 3h;
(4) gained reactant soaks and dialyses 3 days in deionized water, changes twice water every day, uses above-mentioned dialysis tubing.Obtain the magnetic hydrogel of fabricated in situ, be numbered d, as shown in Figure 1.
By embodiment 1 ~ 4, successfully prepare copolymer hydrogel and synthesizing magnetic particle Fe therein 3o 4, pictorial diagram as shown in Figure 1.To sample a ~ d in embodiment 1 ~ 4, dynamic light scattering (DLS) test is carried out in sampling, and draws Fig. 2 according to dispersed test result, makes Fig. 3 according to particle diameter raw data.The hydrogel being respectively a ~ d by numbering in Example 1 ~ 4 carries out lyophilize process, and then sample a and d and carry out Fourier transform infrared spectroscopy (FT-IR) test, sampling c and d carries out x-ray fluorescence analyzer (XRD) test.Characterize in FT-IR spectrogram (Fig. 4) in copolymer hydrogel a and contain NtBAM and AAc two kinds of monomer components, and owing to comprising Fe-O key in magnetic hydrogel d, thus cause the N-H (3078cm caused in P (NtBAM-co-AAc) -1) key offsets, fail to present peak figure in d.All occur spike in 2 θ close positions in the spectrogram of magnetic hydrogel c and d in XRD spectra (Fig. 5), and position just in time corresponds to Fe 3o 4(220), (311), (400) of lattice, (422), (511), (400) crystal face (standard comparison card JCPDS file#88-0315), characterize Fe 3o 4the existence of crystal.Sample sample c and d in embodiment 3 and 4, carry out inductively coupled plasma atomic emission spectrometry (ICP-AES) test, in sample, Fe particle content as shown in Figure 6.

Claims (11)

1. a magnetic acrylic amide hydrogel, is characterized in that, described hydrogel is by gathering (N-tertiary butyl acrylamide-co-vinylformic acid) P (NtBAM-co-AAc) coated Fe 3o 4particle obtains.
2. a kind of magnetic acrylic amide hydrogel according to claim 1, it is characterized in that, described P (NtBAM-co-AAc) comprises repeating unit A and repeating unit B; Wherein the structural formula of A is b structural formula is
3. a preparation method for magnetic acrylic amide hydrogel, comprising:
(1) monomer N tert butyl acrylamide, monomeric acrylic, emulsifying agent and linking agent are dissolved in deionized water, under nitrogen atmosphere, under 15-40 DEG C of condition, stir, be warming up to 60-90 DEG C, insulation, then initiator is added, continue reaction 0.5-10h, dialysis, obtains compolymer/nano hydrogel; Wherein, monomeric acrylic accounts for the 5%-50% of monomer integral molar quantity;
(2) above-mentioned compolymer/nano hydrogel is adjusted pH to 5.5 ± 1.5, add FeSO 47H 2o, at N 24-24h is stirred, dialysis 0.5-5h, N under atmosphere 2stir 2 ~ 4h under atmosphere, add NaNO 2solution and NH 3h 2o, reaction 2-10h, namely dialysis treatment obtains magnetic Nano hydrogel; Wherein, FeSO 47H 2the add-on of O is the 0.01%-10% of compolymer/nano hydrogel quality summation.
4. the preparation method of a kind of magnetic acrylic amide hydrogel according to claim 3, is characterized in that, in described step (1), the total amount of monomer N tert butyl acrylamide and monomeric acrylic is 0.5 ~ 5g.
5. the preparation method of a kind of magnetic acrylic amide hydrogel according to claim 3, is characterized in that, in described step (1), emulsifying agent is sodium lauryl sulphate, and add-on is the 0.1%-20% of monomer mass summation.
6. the preparation method of a kind of magnetic acrylic amide hydrogel according to claim 3, is characterized in that, in described step (1), linking agent is N, N '-methylene-bisacrylamide, add-on is the 1%-30% of monomer mass summation.
7. the preparation method of a kind of magnetic acrylic amide hydrogel according to claim 3, is characterized in that, in described step (1), initiator is ammonium persulphate, and add-on is the 0.1%-10% of monomer mass summation.
8. the preparation method of a kind of magnetic acrylic amide hydrogel according to claim 3, is characterized in that, in described step (1), churning time is 30-120min.
9. the preparation method of a kind of magnetic acrylic amide hydrogel according to claim 3, is characterized in that, in described step (1), soaking time is 30-60min.
10. the preparation method of a kind of magnetic acrylic amide hydrogel according to claim 3, is characterized in that, NaNO in described step (2) 2add-on be the 0.001%-1% of compolymer/nano hydrogel quality summation; The add-on of ammoniacal liquor is the 1%-25% of compolymer/nano hydrogel quality summation.
The preparation method of 11. a kind of magnetic acrylic amide hydrogels according to claim 3, it is characterized in that, dialyse as adopting deionized water to soak 4-8 days in described step (1) and step (2), change twice water every day, the molecular weight cut-off of dialysis tubing used is 8000-14000.
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CN110479385A (en) * 2019-08-22 2019-11-22 浙江理工大学 A kind of hud typed Fe that cladding size is controllable3O4The preparation method of@hydrogel nanocatalyst
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CN112812328A (en) * 2021-02-09 2021-05-18 安徽美科迪智能微胶囊科技有限公司 Copolymerization nano hydrogel capable of thermally induced in-situ gelation and preparation method thereof
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