CN109400916A - A kind of SiO2Luminous hydrogel material of graft polymers and preparation method thereof - Google Patents
A kind of SiO2Luminous hydrogel material of graft polymers and preparation method thereof Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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Abstract
The invention discloses a kind of SiO2Luminous hydrogel material of graft polymers and preparation method thereof, first to SiO2Surface is modified, and the PEG of low molecular weight is then grafted, so that SiO2It is added in hydrogel in the form of monomer.This method not only increases swelling behavior and improves its mechanical performance.It is directed to shining for hydrogel, present invention iminodiacetic acid (IDA) can issue the light of different colours as rare earth ligand, adjusting different rare earth ion proportions.And due to SiO in hydrogel2- PEG's improves rare earth luminous stability there are a degree of.
Description
Technical field
The present invention relates to PEG hydrogel illumination field, especially a kind of SiO2The luminous hydrogel material of graft polymers
And preparation method thereof.
Background technique
Macromolecule hydrogel is a kind of high molecular material that can largely absorb water in its three-dimensional net structure.Rare earth ion
Make rare earth organic fluorescent materials that there is luminous intensity height, pure color, the high spectral line of fluorescence efficiency with distinct electrical sublayer structure
The advantages that abundant, and luminescent color and the environment where rare earth ion are substantially unrelated, depend primarily on rare earth ion itself.Mesh
Before, the gel rubber system that can be shone, which has Metallogels based on organic light emission system and mainly with macromolecule hydrogel, is
The recombination luminescence aquogel system of main body.Luminescent Material of Rare Earth Polymer has compared to rare earth small molecule emitter material in recent years
The advantages that abundant raw material, stability is good, light weight, processing and forming at low cost are easy, thus rare earth small molecule emitter material is high
Molecularization is research hotspot in recent years.Rare earth europium complex is a kind of high luminous quantum efficiency for having both organic compound and nothing
The red fluorescence material of machine compound good stability, has a good application prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of SiO2It is grafted SiO2Generate SiO2- PEG is monomer, hydridization luminophore
It is added thereto, obtains the macromolecular LED hydrogel that a kind of intensity is high, light is stable.
To realize above-mentioned technical purpose and the technique effect, technical solution of the present invention are as follows:
A kind of SiO2The preparation method of the luminous hydrogel material of graft polymers, comprising the following steps:
Step 1 prepares SiO2It is grafted polyethylene glycol:
2. the preparation of chlorine silicon ball
3.0g nano silica is added in the three-necked flask of 250mL, the nano silica is in vacuum drying oven
At 80 DEG C, prebake 24 hours, 25mL benzene is added and makes it dissolve, nitrogen protection, and 25mL dichloro is added dropwise by separatory funnel
Sulfoxide has HCl and SO with that2It generates, 65 degrees Celsius are reacted 4 hours；Then reaction mixture is centrifugated, 7000r/
Min, 7min；And it is washed three times with benzene, the chlorine silicon ball vacuum drying that will be obtained, and be stored in closed container；
2. silica surface is grafted PEG
2.0g chlorine silicon ball is added in 20mL toluene, in the poly- second two for the low molecular weight that 20mL is added under magnetic agitation
Alcohol, 65 degrees Celsius of nitrogen protection are reacted 5 hours；It is finally centrifugated reaction mixture, 7000r/min, 7min, and is washed with toluene
It washs twice, to remove unreacted PEG, when centrifuge separation twice with acetone washing；Vacuum drying products obtained therefrom；
Step 2 prepares the carrier IDHPMA that shines
Iminodiacetic acid (IDA) is grafted to methyl propenoic acid glycidyl by the ring-opening reaction of epoxide moiety
On ester (GMA), organic matter IDHPMA is obtained；Before IDA and copolymer reaction, in excessive KOH aqueous solution and IDA is to keep away
Exempt from carboxylic acid and epoxy reaction；It takes a certain amount of GMA and IDA dipotassium saline solution to be added in quantitative methanol, flows back 3 at 65 DEG C
Hour, after reaction, polymer solution precipitates in cold ether；Then it is washed with tetrahydrofuran and hexane 24 hours dry；
Step 3: preparing the luminous hydrogel that Re-IDA coordination ratio is 1:3: first by the SiO of 0.1g2- PEG, 0.1g
IDHPMA and the acrylamide of 0.1g be added in 2.13ml water, 290 μ l 10wt%ReCl are then added3Aqueous solution and total
A small amount of initiator ammonium persulfate, promotor four is added in reaction vessel in the N of monomer weight 5%, N- methylene-bisacrylamide
Methyl ethylenediamine is stirred, and last mixed solution is placed in 6 DEG C of environment after 72 hours, and mixture becomes uniform hydrogel.
The preparation method: the rare earth ion uses commercially available rare earth oxide ion, ionized to obtain；And rare earth member
Element is one of Eu, Gd, Tb or two kinds.
The preparation method: the nano silica used is commercially available silica, and partial size is 20-200 nanometers,
Benzene, polyethylene glycol, thionyl chloride, iminodiacetic acid, ether, tetrahydrofuran and hexane are analysis net product, metering system
Acid glycidyl ester is 97%, stabilizer containing 100ppmMEHQ.
The preparation method: the molecular weight of the polyethylene glycol (LMPEG) of low molecular weight is PEG200.
The preparation method: the high polymer monomer of the hydrogel is acrylamide and PEG.
The preparation method: rare earth element is two kinds of elements of Gd and Eu in step 3, and the molar ratio of Eu:Gd is 1:0,1:
1, one of 1:3 and 0:1.
The preparation method: in step 3 rare earth element be two kinds of elements of Eu and Tb, Eu:Tb molar ratio be 1:0,1:1,
One of 1:3,1:9,4:96 and 0:1.
The SiO prepared according to any the method2The luminous hydrogel material of graft polymers.
The invention has the following advantages:
(1) due to using SiO2With the method for PEG grafting, SiO2Addition not only play the role of crosslinking agent, but also play
The effect of perforating agent improves the swellability and temperature-responsive (Fig. 2, figure of hydrogel while improving gel mechanical strength
4)。
(2) due to joined SiO2- PEG high molecular material, can be a certain amount of rare earth ion complex compound in hydrogel
It wraps up, plays buffer action, can greatly reduce energy loss caused by vibration relaxation, improve rare earth luminous stabilization
Property.In the luminous hydrogel of storage, SiO is added2The hydrogel of-PEG high molecular material is within the time of 30d, light emission luminance
It is relatively stable lasting.
Detailed description of the invention
Fig. 1 is reaction process schematic diagram of the invention；
Fig. 2 is compression strength of the invention, water content test chart；
(a) is the Nano-meter SiO_2 for not processing modification in Fig. 32IR spectrogram；It (b) is SiO2The IR spectrogram of-PEG；
Fig. 4 is the swellbility and time subduplicate curve graph of hydrogel；
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
(1) SiO is prepared2It is grafted polyethylene glycol (PEG-200):
SiO2It is grafted the preparation of polyethylene glycol:
The preparation of chlorine silicon ball: 3.0g nano silica is added in the three-necked flask of 250mL (80 DEG C in vacuum drying oven
Under, prebake 24 hours), 25mL benzene is added and makes it dissolve, nitrogen protection, and 25ml dichloro Asia is added dropwise by separatory funnel
Sulfone has HCl and SO with that2It generates, 65 degrees Celsius are reacted 4 hours.Then reaction mixture is centrifugated, 7000r/
Min, 7min.And it is washed three times with benzene, the chlorine silicon ball vacuum drying that will be obtained, and be stored in closed container.
Silica surface is grafted PEG-200: 2.0g chlorine silicon ball being added in 20mL toluene, is being added under magnetic agitation
20mLPEG (200), 65 degrees Celsius of nitrogen protection are reacted 5 hours.Finally it is centrifugated reaction mixture, 7000r/min, 7min,
And washed twice with toluene, to remove unreacted PEG, when centrifuge separation twice with acetone washing.Vacuum drying products obtained therefrom.
As shown in figure 3, a is the Nano-meter SiO_2 for not processing modification in Fig. 32IR spectrogram, theoretically for, in 3750cm-1
The characteristic absorption peak of Si-OH should occur in place, and in fact, it will be seen that instead in 3420cm-1Place is shown
The absorption peak of protrusion, this is by Nano-meter SiO_22Caused by silicone hydroxyl is combined with the surface the anti-hydroxyl stretching vibration of water, Si-OH is shielded
Original absorption peak.In addition, 1628cm-1Place be also water absorption peak, specifically with free water (pore water and surface physics
Adsorb water) absorption peak that generates of the bending vibration of related hydrogen-oxygen-hydrogen bond.1110cm-1The narrower and strong peak of attachment is nanometer two
The significant peak of silica, this peak are the absorption peak generated by silicon-oxygen-silicon symmetrical stretching vibration, 786cm-1Place is by silicon-oxygen-
The absorption peak that the antisymmetric stretching vibration of silicon generates, 467cm-1For silicon-oxygen-silicon bending vibration absorption peak.In curve b, remove
There is Nano-meter SiO_22Absorption peak outside, while in 2920cm-1There is characteristic peak in place, this peak is attributed to SiO2The PEG on surface
The stretching vibration absworption peak of methylene, SiO2- PEG is in 1100cm-1Characteristic peak ratio SiO at left and right2Obviously broaden, this is
Due to carbon-oxygen-carbon, silicon-oxygen-carbon, the respective symmetrical stretching vibration characteristic peak of silicon-oxygen-silicon this position be overlapped mutually as a result,
Above analytical proof nano silicon spheres surface is attached with PEG.
(2) preparation of luminous carrier IDHPMA
Iminodiacetic acid (IDA) is grafted to methyl propenoic acid glycidyl by the ring-opening reaction of epoxide moiety
On ester (GMA), organic matter IDHPMA is obtained.Before IDA and copolymer reaction, in excessive KOH aqueous solution and IDA is to keep away
Exempt from carboxylic acid and epoxy reaction.It takes a certain amount of GMA and IDA dipotassium saline solution to be added in quantitative methanol, flows back 3 at 65 DEG C
After the reaction of hour, polymer solution precipitates in cold ether.Then it is washed with tetrahydrofuran and hexane 24 hours dry.
(3) the luminous hydrogel that Eu (Gd, Tb)-IDA coordination ratio is 1:3 is prepared, first by the SiO of 0.1g2-PEG
(200), the acrylamide of the IDHPMA and 0.1g of 0.1g are added in 2.13ml water, and 290 μ l10wt%EuCl are then added3
(or Gd Cl3、TbCl3) aqueous solution and total monomer weight 5% N, N- methylene-bisacrylamide is added few in a bottle
Amount initiator ammonium persulfate, promotor tetramethylethylenediamine are stirred, and last mixed solution is placed in 6 DEG C of environment 72 hours
Afterwards, mixture becomes uniform hydrogel.
(4) by step (3) obtain composite hydrogel is placed under the ultraviolet lamp of 365nm, containing only Eu rare earth element must answer
Heshui gel is red, contains only Gd rare earth element and obtains composite hydrogel as blue, contains only Tb rare earth element and obtain compound water congealing
Glue is green.
Figure 4, it is seen that difference SiO2When the hydrogel of-PEG freeze-drying is swollen in water, just start hydrogel
Quickly, the rising being of a straight line type, water constantly enters swellbility inside hydrogel network and is continuously increased the rate of swelling.And with molten
The swollen time is continuously increased, and swelling rate starts to tend towards stability, and when moisture disengaging gel reaches balance, swelling rate is almost
Zero, the swellbility of hydrogel is no longer changed.In hydrogel, because of SiO2There are many hydroxyls on surface, can and acryloyl
The amido of amine forms hydrogen bond action, so Nano-meter SiO_22It can play the role of Physical crosslinking agent in hydrogel.Due to SiO2-
The presence of PEG in PEG macromolecule has in the inside of hydrogel many larger in this way so that the crosslink density of hydrogel is lower
Hole.Moisture spread from hydrogel mainly by cavity diffusion, so the swelling behavior rate of high molecular weight PEGs compared with
Fastly, swellbility is larger.As PEG molecular weight must be reduced, polymer network just will form even closer structure, between hydrogel
Hole reduce water be not easy inwardly to spread, the swelling rate and swellbility of hydrogel can all reduce.Due to crosslink density obtain it is former
Cause, as seen from Figure 4, compression strength SiO2- PEG (200) has and obvious must increase.
Embodiment 2
By method and steps described in embodiment 1, what is only prepared in step (3) is containing two kinds of elements of Gd and Eu.?
Under the ultraviolet lamp of 365nm, wherein containing only the composite hydrogel of Gd rare earth element as blue, the compound of Eu rare earth element is contained only
Hydrogel is red.When wherein containing two kinds of rare earth elements of Eu and Gd, the molar ratio of Eu and Gd are 1:0,1:1,1:3 and 0:1
When, color change difference red, purple, reddish violet and the blue of composite hydrogel.
Embodiment 3
By method and steps described in embodiment 1, what is only prepared in step (3) is containing two kinds of elements of Eu or Tb.?
Under the ultraviolet lamp of 365nm, wherein containing only the composite hydrogel of Tb rare earth element as green, the compound of Eu rare earth element is contained only
Hydrogel is red.When wherein containing two kinds of rare earth elements of Eu and Tb, when Eu:Tb molar ratio is 1:0,1:1,1:3,1:9,4:96
When with 0:1, color change difference red, pink colour, pale pink, white, light green color and the green of composite hydrogel.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (8)
1. a kind of SiO2The preparation method of the luminous hydrogel material of graft polymers, which comprises the following steps:
Step 1 prepares SiO2It is grafted polyethylene glycol:
1. the preparation of chlorine silicon ball
3.0g nano silica is added in the three-necked flask of 250mL, the nano silica is 80 DEG C in vacuum drying oven
Under, prebake 24 hours, 25mL benzene is added and makes it dissolve, nitrogen protection, and 25mL thionyl chloride is added dropwise by separatory funnel,
HCl and SO are had with that2It generates, 65 degrees Celsius are reacted 4 hours；Then reaction mixture is centrifugated, 7000r/min,
7min；And it is washed three times with benzene, the chlorine silicon ball vacuum drying that will be obtained, and be stored in closed container；
2. silica surface is grafted PEG
2.0g chlorine silicon ball is added in 20mL toluene, in the polyethylene glycol for the low molecular weight that 20mL is added, nitrogen under magnetic agitation
65 degrees Celsius of gas shielded are reacted 5 hours；It is finally centrifugated reaction mixture, 7000r/min, 7min, and washs two with toluene
It is secondary, to remove unreacted PEG, when centrifuge separation twice with acetone washing；Vacuum drying products obtained therefrom；
Step 2 prepares the carrier IDHPMA that shines
Iminodiacetic acid (IDA) is grafted to glycidyl methacrylate by the ring-opening reaction of epoxide moiety
(GMA) on, organic matter IDHPMA is obtained；Before IDA and copolymer reaction, in excessive KOH aqueous solution and IDA to avoid
Carboxylic acid and epoxy reaction；A certain amount of GMA and IDA dipotassium saline solution is taken to be added in quantitative methanol, reflux 3 is small at 65 DEG C
When, after reaction, polymer solution precipitates in cold ether；Then it is washed with tetrahydrofuran and hexane 24 hours dry；
Step 3: the luminous hydrogel that Re-IDA coordination ratio is 1:3 is prepared: first by the SiO of 0.1g2- PEG, 0.1g's
The acrylamide of IDHPMA and 0.1g is added in 2.13ml water, and 290 μ l 10wt%ReCl are then added3Aqueous solution and total list
A small amount of initiator ammonium persulfate, promotor tetramethyl is added in reaction vessel in the N of body weight 5%, N- methylene-bisacrylamide
Base ethylenediamine is stirred, and last mixed solution is placed in 6 DEG C of environment after 72 hours, and mixture becomes uniform hydrogel.
2. preparation method as described in claim 1, it is characterised in that: the rare earth ion uses commercially available rare earth oxide ion,
It is ionized to obtain；And rare earth element is one of Eu, Gd, Tb or two kinds.
3. preparation method as described in claim 1, it is characterised in that: the nano silica used is commercially available titanium dioxide
Silicon, partial size are 20-200 nanometers, and benzene, polyethylene glycol, thionyl chloride, iminodiacetic acid, ether, tetrahydrofuran and hexane are
Analyze net product, glycidyl methacrylate 97%, stabilizer containing 100ppmMEHQ.
4. preparation method as described in claim 1, it is characterised in that: the molecular weight of the polyethylene glycol (LMPEG) of low molecular weight
For PEG200.
5. preparation method as described in claim 1, it is characterised in that: the high polymer monomer of the hydrogel be acrylamide and
PEG。
6. preparation method as described in claim 1, it is characterised in that: rare earth element is two kinds of elements of Gd and Eu in step 3,
The molar ratio of Eu:Gd is one of 1:0,1:1,1:3 and 0:1.
7. preparation method as described in claim 1, it is characterised in that: rare earth element is two kinds of elements of Eu and Tb in step 3,
Eu:Tb molar ratio is one of 1:0,1:1,1:3,1:9,4:96 and 0:1.
8. the SiO of -7 any the method preparations according to claim 12The luminous hydrogel material of graft polymers.
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| CN110527118A (en) * | 2019-07-11 | 2019-12-03 | 宁波大学 | A kind of humidity fluorescent color responsive polymer elastomer thin film material and preparation method thereof |
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| CN110522951A (en) * | 2019-09-11 | 2019-12-03 | 湖南工业大学 | It is a kind of with antifatigue and impact property gel rubber material |
| CN110522951B (en) * | 2019-09-11 | 2021-08-27 | 湖南工业大学 | Gel material with anti-fatigue and anti-impact characteristics |
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| CN109400916B (en) | 2021-01-12 |
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