CN108424522B - A kind of nano-cellulose/poly-dopamine/polyethylene glycol composite material and preparation method - Google Patents
A kind of nano-cellulose/poly-dopamine/polyethylene glycol composite material and preparation method Download PDFInfo
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- CN108424522B CN108424522B CN201810331559.0A CN201810331559A CN108424522B CN 108424522 B CN108424522 B CN 108424522B CN 201810331559 A CN201810331559 A CN 201810331559A CN 108424522 B CN108424522 B CN 108424522B
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Abstract
The present invention discloses a kind of nano-cellulose/poly-dopamine/polyethylene glycol composite material, by the surface of nano-cellulose through poly-dopamine modified lithium, then is grafted polyethylene glycol and is made, and polyethylene glycol is the polyethylene glycol of amino or sulfhydrylation modification and methoxy group.Its corresponding preparation method is provided simultaneously.Nano-cellulose/poly-dopamine/polyethylene glycol composite material of the invention can be scattered in again in water, N ' dinethylformamide, dimethyl sulfoxide or ethyl alcohol isopolarity solvent, good dispersion occurs without sedimentation phenomenon, thermostabilization is good, and since composite material is limited only to be modified the surface of nano-cellulose (CNCs), the nanocrystalline structure of CNCs is unaffected.
Description
Technical field
The invention belongs to nanocomposite technical fields, and in particular to a kind of nano-cellulose/poly-dopamine/poly- second two
Alcohol composite material and preparation method.
Background technique
Nano-cellulose (Cellulose nanocrystal body, Cellulose Nanocrystals, CNCs) is a kind of length several
Hundred nanometers, width be tens nanometers spindle-type, high length-diameter ratio monodimension nanometer material, usually by microcrystalline cellulose through strong acid water
It is made after solution.CNCs has Young's modulus, tensile strength and the extremely low thermal expansion coefficient of superelevation, can be used as a kind of high-performance material
Expect reinforcing agent, has in terms of gel rubber material, membrane material, high-molecular biologic potential using (Habbi Y, et
Al., Chemical Reviews, 2010,110 (6), 3479-3500).However, since the surface CNCs is rich in hydroxyl, pole
Property it is high, hydrogen bond action is strong, irreversible reunion easily occur, causes it that can not effectively be distributed in matrix to be reinforced, and more
Be to save and use in the form of suspension, and then limit its extensive use.
Summary of the invention
It is an object of that present invention to provide a kind of nano-cellulose/poly-dopamine/polyethylene glycol composite materials, while providing it
Corresponding preparation method is another goal of the invention of the invention.
Based on above-mentioned purpose, the present invention takes following technical scheme:
A kind of nano-cellulose/poly-dopamine/polyethylene glycol composite material, by the surface of nano-cellulose through poly- DOPA
Amine is modified, then is grafted polyethylene glycol and is made, and polyethylene glycol is the polyethylene glycol of amino or sulfhydrylation modification and methoxy group.
The nano-cellulose, poly-dopamine, polyethylene glycol mass ratio be (1 ︰ (2-15) of 4-15) ︰.
The molecular weight of the polyethylene glycol is 1000-10000.
Prepare nano-cellulose/poly-dopamine/polyethylene glycol composite material method, comprising the following steps:
1) under stirring condition, alkalescent is successively added into the nano-cellulose aqueous suspension that concentration is 0.2-2wt% and is delayed
Electuary and dopamine hydrochloride mixing, mixed system pH value are greater than 8.5, after reaction, and the reaction time is more than or equal to 12h, are centrifuged, thoroughly
Analysis, when dialysis, molecular cut off 10K-300K obtains nano-cellulose/poly-dopamine suspension；
2) alkalescent buffer is added into the nano-cellulose of step 1)/poly-dopamine suspension, makes mixed system pH
Value stirs 12- at 30-55 DEG C greater than 8.5, to add the polyethylene glycol of amino or sulfhydrylation modification and methoxy group
48h, centrifugation, dialysis, freeze-drying, obtains nano-cellulose/poly-dopamine/polyethylene glycol composite material；When dialysis, molecule is retained
Amount is 10K-300K.
Step 1) and 2) in alkalescent buffer be three (methylol) aminomethanes, centrifugal condition: centrifugal rotational speed 9000-
10000r/min, centrifugation time 10-15min；When step 1) mixing and reaction, speed of agitator is 500-2000 r/min, instead
It is 12-48 h between seasonable.
Step 1) and condition of 2) dialysing: at room temperature, dialyse 24-48h；Step 2 speed of agitator is 100-500 r/min.
Dopamine is a kind of neurotransmitter, contains catechol and amido functional group, can occur in weak alkaline aqueous solution
Auto polymerization reaction is aoxidized, is obtained poly-dopamine (Polydamine, PDA), PDA has strong adhesion, can be in different substrates, very
Coating is formed as super hydrophobic surface, coating layer thickness is controllable, and has very high stability.
PEG is a kind of polymer of electroneutral, is dissolvable in water water and most of organic solvent, has good biofacies
Capacitive, degradability prevent the advantageous properties such as nonspecific proteins absorption, in bio-medical field, such as medicament slow release and development
Etc. used extensively.
Compared with prior art, the invention has the following advantages:
1) nano-cellulose/poly-dopamine/polyethylene glycol composite material of the invention can be scattered in water, N ' N- diformazan again
In base formamide, dimethyl sulfoxide or ethyl alcohol isopolarity solvent, good dispersion occurs without sedimentation phenomenon, and thermostabilization is good, and due to
Composite material is limited only to be modified the surface of nano-cellulose (CNCs), and the nanocrystalline structure of CNCs is unaffected；
2) PDA is covered in CNCs plane of crystal by the present invention, and is introduced amino, imines and catechol etc. on its surface and lived
Property group, it can be achieved that load to metal nanoparticle, and can with the functionalization reactive organic molecule with amino or sulfydryl,
It is further surface-functionalized to be realized to CNCs；The aqueous solution of three (methylol) aminomethanes (TRIS) is molten as buffering
Liquid can form mild alkaline conditions, facilitate the progress of graft reaction；
3) present invention first prepares the CNCs of PDA functionalization, then by the PEG-SH of different molecular weight or PEG-NH2Lead to respectively
Crossing Michael addition reaction (Michael addition reaction) and seat, not alkali (Schiff base) reactive grafting arrives
The surface CNCs, is utilized the space steric effect of PEG chain segment formation, and the irreversible aggrengation effectivelying prevent between CNCs improves
The dispersibility of CNCs and its cycle-index in vivo is improved, PEG molecular weight is bigger, and the steric effect of formation is stronger, multiple
The dispersibility of condensation material is also better, and reaction efficiency is lower, main reason is that in the case where molecular weight is excessively high, under phase homogenous quantities
The decline of ratio contained by terminal functionality, while being easily embedded in molecule segment, cause reaction efficiency to decrease.The reaction item
Part is mild, the reaction time is short, easy to operate, and the exploitation and preparation to nano-cellulose based composites have important reality meaning
Justice.
Detailed description of the invention
Fig. 1 is CNCs-PDA and CNCs-PDA-PEG2000The photo being dispersed back into after freeze-drying in aqueous solution；
Fig. 2 is CNCs, CNCs-PDA, CNCs-PDA-PEG2000Heat analysis photo；
Fig. 3 is CNCs, CNCs-PDA, CNCs-PDA-PEG2000Zeta potential figure in aqueous solution.
Specific embodiment
Embodiment 1
A kind of nano-cellulose/poly-dopamine/polyethylene glycol composite material, by the surface of nano-cellulose through poly- DOPA
Amine is modified, then is grafted polyethylene glycol and is made, and polyethylene glycol is the polyethylene glycol of amino or sulfhydrylation modification and methoxy group, institute
State nano-cellulose, poly-dopamine, polyethylene glycol mass ratio be the molecular weight of polyethylene glycol described in 5.5 ︰, 1 ︰ 2 be 2000.
Prepare nano-cellulose/poly-dopamine/polyethylene glycol composite material method, comprising the following steps:
1) in 25 DEG C, non-under confined conditions, (namely bottle stopper or open state is not added in reaction vessel, so that subsequent reactions liquid
Face is contacted with air always, so that oxygen is able to enter reaction system), speed of agitator is to be to 150g concentration under 600 r/min
(diameter of nano-cellulose exists the nano-cellulose aqueous suspension of 0.75wt%: 5~20 nm, length: 200~800 nm, table
1.2 mmol/g of face carboxyl-content) in successively add (methylol) aminomethane of 0.2g tri- and 0.6g dopamine hydrochloride mixing,
Reaction for 24 hours, under centrifugal rotational speed 10000r/min, is centrifuged 10min, and suspension is transferred to bag filter, molecular cut off 300K,
At 25 DEG C, dialyse 24 h, and obtaining concentration is about 0.60% nano-cellulose/poly-dopamine suspension；
2) 0.1g tri- (methylol) amino is successively added into the nano-cellulose of 20g step 1)/poly-dopamine suspension
The polyethylene glycol (molecular weight Mw=2000) of methane and 0.2g amination modification and methoxy group is in 55 DEG C, speed of agitator
Under 400 r/min, 12h is stirred, by reaction solution at centrifugal rotational speed 10000r/min, 10min is centrifuged, is transferred to bag filter, retain
Molecular weight is 10K, and at 25 DEG C, dialyse 24 h, during which can repeatedly replace dialyzate (dialyzate is deionized water), obtain Nanowire
Element/poly-dopamine/polyethylene glycol suspensoid is tieed up, (condition: vacuum degree is 0.02 mbar, condenser temperature is -53 for freeze-drying
DEG C, time 48h), obtain nano-cellulose/poly-dopamine/polyethylene glycol composite material.
Embodiment 2
A kind of nano-cellulose/poly-dopamine/polyethylene glycol composite material, by the surface of nano-cellulose through poly- DOPA
Amine is modified, then is grafted polyethylene glycol and is made, and polyethylene glycol is the polyethylene glycol of amino or sulfhydrylation modification and methoxy group, institute
State nano-cellulose, poly-dopamine, polyethylene glycol mass ratio be 5.5 ︰, 1 ︰ 3.2；The molecular weight of the polyethylene glycol is 5000.
Prepare nano-cellulose/poly-dopamine/polyethylene glycol composite material method, comprising the following steps:
1) in 25 DEG C, non-under confined conditions, (namely bottle stopper or open state is not added in reaction vessel, so that subsequent reactions liquid
Face is contacted with air always, so that oxygen is able to enter reaction system), speed of agitator is to be to 150g concentration under 600 r/min
Nano-cellulose aqueous suspension (the diameter of nano-cellulose: 5~20 nm, length: 200~800 nm, surface of 0.75wt%
1.2 mmol/g of carboxyl-content) in successively add (methylol) aminomethane of 0.2g tri- and 0.6g dopamine hydrochloride mixing, instead
It should be centrifuged 10min for 24 hours, under centrifugal rotational speed 10000r/min, suspension is transferred to bag filter, molecular cut off 300K, in
At 25 DEG C, dialyse 24 h, and obtaining concentration is 0.60% nano-cellulose/poly-dopamine suspension；
2) 0.2g tri- (methylol) amino is successively added into the nano-cellulose of 40g step 1)/poly-dopamine suspension
The polyethylene glycol (molecular weight Mw=5000) of methane and 0.8g amination modification and methoxy group is in 55 DEG C, speed of agitator
Under 500 rpm, 12h is stirred, by reaction solution at centrifugal rotational speed 10000r/min, is centrifuged 15min, is transferred to bag filter, retention point
Son amount is 300K, and at 25 DEG C, dialyse 48 h, during which can repeatedly replace dialyzate (deionized water), obtains nano-cellulose/poly- more
Bar amine/polyethylene glycol suspensoid, freeze-drying (vacuum degree is 0.02 mbar, condenser temperature is -53 DEG C, time 48h), must receive
Rice cellulose/poly-dopamine/polyethylene glycol composite material.
Embodiment 3
A kind of nano-cellulose/poly-dopamine/polyethylene glycol composite material, by the surface of nano-cellulose through poly- DOPA
Amine is modified, then is grafted polyethylene glycol and is made, and polyethylene glycol is the polyethylene glycol of amino or sulfhydrylation modification and methoxy group, institute
State nano-cellulose, poly-dopamine, polyethylene glycol mass ratio be 10 ︰, 1 ︰ 4；The molecular weight of the polyethylene glycol is 5000.
Prepare nano-cellulose/poly-dopamine/polyethylene glycol composite material method, comprising the following steps:
1) in 25 DEG C, non-under confined conditions, (namely bottle stopper or open state is not added in reaction vessel, so that subsequent reactions liquid
Face is contacted with air always, so that oxygen is able to enter reaction system), speed of agitator is to be to 140g concentration under 600 r/min
Nano-cellulose aqueous suspension (the diameter of nano-cellulose: 5~20 nm, length: 200~800 nm, surface of 1.0 wt%
1.2 mmol/g of carboxyl-content) in successively add (methylol) aminomethane of 0.2g tri- and 0.3g dopamine hydrochloride mixing, instead
It should be centrifuged 10min for 24 hours, under centrifugal rotational speed 10000r/min, suspension is transferred to bag filter, molecular cut off 50K, in
At 25 DEG C, dialyse 24 h, obtains nano-cellulose/poly-dopamine suspension that concentration is 0.55wt%；
2) 0.2g tri- (methylol) amino is successively added into the nano-cellulose of 30g step 1)/poly-dopamine suspension
The polyethylene glycol (molecular weight Mw=5000) of methane and 0.6g sulfydryl modification and methoxy group, in 30 DEG C, speed of agitator 500
Under rpm, 48h is stirred, by reaction solution at centrifugal rotational speed 10000r/min, 15min is centrifuged, suspension is transferred to bag filter, cut
Staying molecular weight is 300K, and at 25 DEG C, dialyse 48 h, during which can repeatedly replace dialyzate (dialyzate is deionized water), must receive
Rice cellulose/poly-dopamine/polyethylene glycol suspensoid, freeze-drying (vacuum degree is 0.02 mbar, and condenser temperature is -53 DEG C,
Dry 48h), obtain nano-cellulose/poly-dopamine/polyethylene glycol composite material.
4 phenetic analysis of embodiment
The test of 4.1 dispersion performances
By nano-cellulose/poly-dopamine/polyethylene glycol (CNCs-PDA-PEG) composite material obtained in embodiment 1 and
The nano-cellulose of step 1)/poly-dopamine suspension obtained by freeze drying nano-cellulose/poly-dopamine composite material
(CNCs-PDA) it is added separately in deionized water, ultrasonic disperse 30 minutes, stands 2 minutes, shoot photo, as shown in Figure 1.
As shown in Figure 1, CNCs-PDA compound after drying can not effectively disperse again, settle out immediately after standing
Existing, solution is substantially colorless, and CNCs-PDA-PEG favorable dispersibility, occurs after standing without sedimentation phenomenon, and can keep for a long time equal
Phase is brown color suspension.
4.2 heat analysis
To CNCs-PDA, CNCs-PDA- of step 1) obtained by freeze drying in nano-cellulose (CNCs), embodiment 1
PEG carries out heat analysis.Test equipment is U.S. TA company SDT-Q600 synchronous solving, and heating rate is 10 K/min, nitrogen
Atmosphere is enclosed, and it is as shown in Figure 2 to test resulting thermogravimetric (TG) curve.Fig. 2 (a) is the matter of CNCs, CNCs-PDA, CNCs-PDA-PEG
Measure thermogravimetric (TG) curve varied with temperature；Fig. 2 (b) is that TG curve does the differential that once differentiation is calculated to time reference axis
Curve, i.e. DTG curve.
By Fig. 2 (a) it is found that CNCs-PDA thermal decomposition temperature is higher than CNCs, and the thermal decomposition temperature of CNCs-PDA-PEG is high
In CNCs-PDA；Fig. 2 (b) is it is found that CNCs, CNCs-PDA, CNCs-PDA-PEG mass rate variation maximum point are respectively 331
DEG C, 340 DEG C, 407 DEG C be especially grafted upper PEG it follows that thermal stability is significantly improved after CNCs is surface-functionalized
Afterwards, mass rate variation maximum point is increased to 407 DEG C from 340.
4.3 dispersibility characterizations
The dispersibility of CNCs, CNCs-PDA and CNCs-PDA-PEG suspension in embodiment 1 is tested, test equipment
Wave nanometers of dynamics of Nanotrac and surface of solids Zeta potential analyzer of Microtrac company, U.S. production.Zeta electricity
The surface electrification of position characterization sample.The test concentrations range of all samples measures sample Zeta electricity in 0.02 ~ 2wt%, pH=7.4
Position, the test value for choosing multiple concentration are averaging, and Zeta potential value is as shown in Figure 3.
From the figure 3, it may be seen that with the surface-functionalized progress from PDA to PEG of CNCs, CNCs, CNCs-PDA and CNCs-PDA-
The Zeta potential of PEG suspension is stepped up from -53 ± 2 mv, -38 ± 1.5 mv, -26 ± 1.5 mv, shows the surface CNCs
It is modified successfully.This is because CNCs and its surface-functionalized CNCs have negative electrical charge.Negative electrical charge mostlys come from CNCs table
The carboxylic acid group in face can allow between CNCs since electrical charge rejection acts on, not assemble.
Claims (6)
1. a kind of nano-cellulose/poly-dopamine/polyethylene glycol composite material, which is characterized in that its by nano-cellulose table
Face is through poly-dopamine modified lithium, then is grafted polyethylene glycol and is made, and polyethylene glycol is amino or sulfhydrylation modification and methoxy group
Polyethylene glycol.
2. nano-cellulose/poly-dopamine/polyethylene glycol composite material as described in claim 1, which is characterized in that described to receive
Rice cellulose, poly-dopamine, polyethylene glycol mass ratio be (1 ︰ (2-15) of 4-15) ︰.
3. nano-cellulose/poly-dopamine/polyethylene glycol composite material as described in claim 1, which is characterized in that described poly-
The molecular weight of ethylene glycol is 1000-10000.
4. any nano-cellulose/poly-dopamine/polyethylene glycol composite material method of claim 1-3 is prepared,
It is characterized in that, comprising the following steps:
1) under stirring condition, alkalescent buffer is successively added into the nano-cellulose aqueous suspension that concentration is 0.2-2wt%
It being mixed with dopamine hydrochloride, mixed system pH value is greater than 8.5, and the reaction time is more than or equal to 12h, after reaction, centrifugation, dialysis,
When dialysis, molecular cut off 10K-300K obtains nano-cellulose/poly-dopamine suspension；
2) alkalescent buffer is added into the nano-cellulose of step 1)/poly-dopamine suspension, keeps mixed system pH value big
In 8.5, the polyethylene glycol for adding amino or sulfhydrylation modification and methoxy group stirs 12-48h at 30-55 DEG C, from
The heart, dialysis, freeze-drying obtain nano-cellulose/poly-dopamine/polyethylene glycol composite material；When dialysis, molecular cut off is
10K-300K。
5. preparing nano-cellulose/poly-dopamine/polyethylene glycol composite material method, feature as claimed in claim 4
Be, step 1) and 2) in alkalescent buffer be three (methylol) aminomethanes, centrifugal condition: centrifugal rotational speed 9000-
10000r/min, centrifugation time 10-15min；When step 1) mixing and reaction, speed of agitator is 500-2000 r/min, instead
It is 12-48 h between seasonable.
6. as claimed in claim 4 prepare nano-cellulose/poly-dopamine/polyethylene glycol composite material method, feature exists
In step 1) and condition of 2) dialysing: at room temperature, dialyse 24-48h；Step 2 speed of agitator is 100-500 r/min.
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| CN113166456A (en) * | 2018-11-30 | 2021-07-23 | 埃森提姆公司 | Hydrophobic modification process in nano-cellulose manufacturing process |
| CN111803629A (en) * | 2020-06-02 | 2020-10-23 | 南京邮电大学 | Organic-inorganic hybrid multifunctional biological material based on nano cellulose crystals and preparation method and application thereof |
| CN113197843A (en) * | 2021-04-30 | 2021-08-03 | 南京林业大学 | Dopamine-coated cellulose nanocrystal-agarose drug-loaded hydrogel and preparation method thereof |
| CN114246181B (en) * | 2021-12-27 | 2023-06-13 | 华南师范大学 | Antibacterial material and preparation method and application thereof |
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