CN110408050A - Cellulose base graft modification reversible gel and preparation method thereof - Google Patents
Cellulose base graft modification reversible gel and preparation method thereof Download PDFInfo
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- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/005—Crosslinking of cellulose derivatives
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- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
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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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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Abstract
The invention discloses a kind of cellulose base graft modification reversible gels and preparation method thereof.After the method is pre-processed cellulose, it is added in organic solvent and forms suspension, suspension is subjected to esterification, it is centrifuged repeatedly purifying in a solvent, obtain the modified cellulose of surface modified end double bond, then again by sulfydryls more in modified cellulose surface modification, the cellulose of sulfydryls more in surface modification is aoxidized at 30~120 DEG C finally and obtains within 6~120 hours cellulose base graft modification reversible gel.Gel produced by the present invention can become suspension under reducing agent effect, become gel again by oxidation.Raw material sources of the present invention are safe and environment-friendly, product has very excellent biocompatibility, gel mechanical strength with higher obtained and reversible performance, and there is hypotoxicity and biocompatibility, it can be widely used for biological medicine, target medicament slow release, the fields such as control switch reactor and recyclable soft material.
Description
Technical field
The present invention relates to the gels that a kind of organic matter is matrix, and in particular to a kind of cellulose base graft modification reversible gel
And preparation method thereof, belong to gel preparation technical field.
Background technique
Gel is a kind of by with the high molecular material of three-dimensional net structure, having very high obtained from appropriately crosslinked
Solvent capacity and flexible natural characteristic, but not it is dissolved in solvent, there is good biocompatibility.In addition, gel has
Porous structure is very suitable to embed biologically active substance.The interaction force of gel and drug molecule is weaker, keeps medicine
While object activity, the swelling behavior of regularity also gives its controlled release to drug.In addition, gel is with good
Structural controllability.Therefore, gel is discharged in organizational project, drug conveying with control as a kind of novel biomaterial for medical purpose
Equal fields have broad application prospects.Especially there is stimulating responsive (such as pH, temperature and redox responsiveness) gel
Great clinical value.
The gel of redox response is one of hot spot of Recent study, wherein most representative is comprising disulfide bond
Gel.Disulfide bond is widely present in human body, and one of most important reaction is exactly the formation and fracture of disulfide bond in human body.Also
Under originality environment, disulfide bond can be reduced into mercaptan；And under oxidative environment, two mercaptan can be oxidized generation two again
Sulfide linkage.(Fairbanks, B.D., the et al.2011, Photodegradable, Photoadaptable such as Fairbanks
Hydrogels via Radical-Mediated Disulfide Fragmentation
Reaction.Macromolecules 44 (8): 2444-2450.) by hydrogen peroxide to the mercaptan oxidation of four kinds of polyethylene glycol
The hydrogel that degradable and light is suitable for is synthesized.(Naga, Naofumi, the Kazumasa Moriyama, and such as Naga
Hidemitsu Furukawa 2017Synthesis and properties of multifunctional thiol
crosslinked gels containing disulfide bond in the network structure.Journal
Of Polymer Science Part A:Polymer Chemistry 55 (22): 3749-3756.) by dimethyl sulfoxide
The middle more mercapto monomers of oxidation obtain the cross-linked gel comprising disulfide bond.But the gel of conventional method preparation cannot combine
The feasibility of excellent mechanical property, good biocompatibility, degradability and large-scale production.
Cellulose as natural high polymer, be by glucose group at a kind of macromolecular polysaccharide, it is not soluble in water and generally have
Solvent.Cellulose has excellent by the crystalline solid (nano-cellulose, CNC) with nano-scale structure that processing obtains
Mechanical property, high-crystallinity, nanometer size effect, good reproducibility and biodegradability.Nano-cellulose can mention
The intensity of high gel, but rely solely on direct filling to prepare plural gel limited to the humidification of the mechanical property of gel.
Summary of the invention
The purpose of the present invention is to provide a kind of cellulose base graft modification reversible gels and preparation method thereof.
Realize that the technical solution of the object of the invention is as follows:
The preparation method of cellulose base graft modification reversible gel, the specific steps are as follows:
Step 1, cellulose is soaked in organic solvent, after ultrasonic disperse is uniform, impregnates 2~8 hours, be centrifuged, repeats
Operation obtains cellulose dispersion liquid to remove impurity；
Step 2, at 25~80 DEG C, by mole of the glucoside unit in cellulose and the acid halide reagents containing terminal olefin
Than the acid halide reagents containing terminal olefin, insulation reaction under stirring condition being slowly added in cellulose dispersion liquid for 1:1~12
It 4~24 hours, is transferred in alcoholic solvent, is centrifuged, repetitive operation obtains sediment, by sediment in swelling agent after reaction
Swelling precipitates centrifugation, the cellulose (E-C) for the surface grafting terminal double bond that repetitive operation is purified in alcoholic solvent；
Step 3, the cellulose of surface grafting terminal double bond and swelling agent are mixed to form to the suspension of 5~40mg/ml,
Molar ratio by glucoside unit and more mercapto reagents in cellulose is 1:1~36, and more mercapto reagents are added into suspension,
It stirs at 20~40 DEG C, and ultraviolet irradiation 1~12 hour, dialyses after reaction, change a solution within every 12~24 hours,
Change 2~4 times, after product centrifugal purification obtained into the cellulose (S-E-C) of the more sulfydryls of surface grafting；
It step 4, is 1:1~24 by the mass ratio of the cellulose of the more sulfydryls of surface grafting and oxidant, surface grafting is more
The cellulose of sulfydryl is immersed in oxidant, and after mixing evenly, sealing is reacted 6~120 hours, is generated cellulose base grafting and is changed
Property reversible gel.
In step 1, the cellulose can be native cellulose, synthetic cellulose etc..Cellulose pattern can be wadding
Shape, membranaceous, whisker, powder etc..The cellulose can be bacteria cellulose, can be the cotton-shaped bacterium that dynamic cultivation obtains
Cellulose is also possible to the powder obtained after the membranaceous cellulose, or both that static culture obtains is ground, or
It is the whisker etc. obtained after hydrolyzing.
In step 1, the organic solvent is selected from pyridine, triethylamine, toluene or aniline, but not limited to this.
In step 2, the molecular formula of the acid halide reagents containing terminal olefin is CH2=CH (CH2)1~10COX, X=
Cl, Br, I, the alcoholic solvent are selected from methanol or ethyl alcohol, but not limited to this, the swelling agent is selected from tetrahydrofuran or third
Ketone, but not limited to this.Swelling agent and alcoholic solvent used in purification process are identical as above-mentioned swelling agent and alcoholic solvent.
In step 3, more mercapto reagents are selected from trimethylolpropane (3-thiopropionate) (TMMP), three-[3- mercaptos
Base propionyloxy-ethyl]-isocyanuric acid ester (TEMPIC), pentaerythrite four (3-thiopropionate) (PEMP), diamyl erythrose
Alcohol six (3-thiopropionate) (DPMP) or tetraethylene glycol bis- (3-thiopropionates) (EGMP-4) and without being limited thereto.
In step 4, when the oxidant is dimethyl sulfoxide (DMSO) or hydrogen peroxide, reaction temperature is 60~120 DEG C,
When the oxidant is selected from the mixing of dimethyl sulfoxide (DMSO) or hydrogen peroxide and acid anhydrides, reaction temperature is 30~90 DEG C.
Compared with prior art, the invention has the following advantages that
The present invention is using cellulose as substrate, in polymer of its surface grafting containing sulfydryl, and aoxidizes to be made and contains disulfide bond
The gel with cross-linked structure, this method raw material is easy to get, safety and environmental protection, and gel obtained has excellent mechanical property
And biocompatibility and redox reversible, it can be widely used for biological medicine, target medicament slow release, control switch reaction
The fields such as device and recyclable soft material.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of cellulose base graft modification reversible gel of the invention；
Fig. 2 is cellulose base graft modification reversible gel pictorial diagram of the invention；
Fig. 3 is the XPS figure of the cellulose of the more sulfydryls of surface modification of the invention.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
Step 1, it weighs 0.8g (dry weight) wadding fibrous element to be soaked in 80ml pyridine, it is small that ultrasonic disperse uniformly impregnates 8 afterwards
When after be centrifuged, repetitive operation obtains cellulose dispersion liquid three times.
Step 2, in the case where temperature is 80 DEG C of stirring conditions, by the glucoside unit and 10- undecene acyl chloride in cellulose
The molar ratio of reagent is 1:1, and 10- undecene acyl chloride reagent is slowly added in cellulose dispersion liquid, is kept the temperature under stirring condition
Reaction 4 hours, is transferred in alcoholic solvent after reaction, is centrifuged, repetitive operation obtains sediment, by sediment in swelling agent
Swelling precipitates centrifugation in alcoholic solvent, the cellulose (E-C) of terminal double bond in the surface modification that repetitive operation is purified.
Step 3, the cellulose of surface grafting terminal double bond and tetrahydrofuran are mixed to form to the suspension solution of 5mg/ml, pressed
The molar ratio of glucoside unit and more mercapto reagents in cellulose is that TMMP is added into suspension by 1:1, is stirred at 40 DEG C, and
Ultraviolet irradiation 12 hours, dialyse after reaction, change a solution within every 12 hours, change 2 times, after product is centrifuged it is pure
Change obtains the cellulose (S-E-C) of the more sulfydryls of surface modification.
It step 4, is 1:1 by the mass ratio of the cellulose of the more sulfydryls of surface grafting and DMSO, by the more sulfydryls of surface grafting
Cellulose is immersed in DMSO, and after mixing evenly, sealing is placed at 60 DEG C and reacts 120 hours, generates cellulose base graft modification
Reversible gel.
Embodiment 2
Step 1,1g cellulose powder is weighed to be added in 50ml triethylamine, after ultrasonic disperse is uniform, impregnate 2 hours after from
The heart, repetitive operation obtain cellulose dispersion liquid to remove undesired impurities.
Step 2, in the case where temperature is 25 DEG C of stirring conditions, by the glucoside unit and 10- undecene acyl chloride in cellulose
Molar ratio be 1:12,10- undecene acyl chloride is slowly added in cellulose dispersion liquid, insulation reaction 24 is small under stirring condition
When, it is transferred in alcoholic solvent, is centrifuged after reaction, repetitive operation obtains sediment, sediment is swollen in acetone, in methanol
Middle precipitating is centrifuged, the cellulose (E-C) of terminal double bond in the surface modification that repetitive operation is purified.
Step 3, the cellulose of surface grafting terminal double bond and acetone are mixed to form to the suspension solution of 40mg/ml, by fibre
The molar ratio of glucoside unit and more mercapto reagents in dimension element is that TEMPIC is added into suspension by 1:36, is stirred at 20 DEG C,
And ultraviolet irradiation 1 hour, dialyse after reaction, change a solution within every 24 hours, change 4 times, after product is centrifuged
Purifying obtains the cellulose (S-E-C) of the more sulfydryls of surface modification.
It step 4, is 1:24 by the mass ratio of the cellulose of the more sulfydryls of surface grafting and DMSO, by the more sulfydryls of surface grafting
Cellulose is immersed in DMSO, and after mixing evenly, sealing is placed at 120 DEG C and reacts 6 hours, generates cellulose base graft modification
Reversible gel；
Embodiment 3
Step 1, it weighs 0.5g cellulose whiskers to be added in 50ml triethylamine, after ultrasonic disperse is uniform, after impregnating 6 hours
Centrifugation, repetitive operation obtain cellulose dispersion liquid to remove undesired impurities；
Step 2, in the case where temperature is 50 DEG C of stirring conditions, by the glucoside unit and 10- undecene acyl chloride in cellulose
Molar ratio be 1:8,10- undecene acyl chloride is slowly added in cellulose dispersion liquid, insulation reaction 7 is small under stirring condition
When, it is transferred in alcoholic solvent, is centrifuged after reaction, repetitive operation obtains sediment, sediment is swollen in acetone, in methanol
Middle precipitating is centrifuged, the cellulose (E-C) of terminal double bond in the surface modification that repetitive operation is purified,
Step 3, the cellulose of surface grafting terminal double bond and acetone are mixed to form to the suspension solution of 20mg/ml, by fibre
The molar ratio of glucoside unit and more mercapto reagents in dimension element is that PEMP is added into suspension by 1:2, is stirred at 25 DEG C, and purple
External exposure 3 hours, dialyse after reaction, change a solution within every 12 hours, change 4 times, after by product centrifugal purification
Obtain the cellulose (S-E-C) of the more sulfydryls of surface modification.
It step 4, is 1:10 by the mass ratio of the cellulose of the more sulfydryls of surface grafting and DMSO, by the more sulfydryls of surface grafting
Cellulose is immersed in DMSO, and after mixing evenly, sealing is placed at 120 DEG C and reacts 16 hours, generates cellulose base graft modification
Reversible gel；
Embodiment 4
Step 1, comminuted fibres element 0.5g is weighed to be soaked in aniline, after ultrasonic disperse is uniform, impregnate 4 hours after from
The heart, repetitive operation obtain cellulose dispersion liquid to remove undesired impurities.
Step 2, in the case where temperature is 60 DEG C of stirring conditions, by the glucoside unit and 10- undecene acyl chloride in cellulose
The molar ratio of reagent is 1:8,10- undecene acyl chloride is slowly added in cellulose dispersion liquid, insulation reaction 7 under stirring condition
Hour, it being transferred in alcoholic solvent, is centrifuged after reaction, repetitive operation obtains sediment, sediment is swollen in swelling agent,
Centrifugation is precipitated in alcoholic solvent, the cellulose (E-C) of terminal double bond in the surface modification that repetitive operation is purified.
Step 3, the cellulose of surface grafting terminal double bond and swelling agent are mixed to form to the suspension solution of 15mg/ml,
Molar ratio by glucoside unit and more mercapto reagents in cellulose is that the reagent containing more sulfydryls is added into suspension by 1:8,
It stirs at 30 DEG C, and ultraviolet irradiation 5 hours, dialyses after reaction, change a solution within every 16 hours, change 3 times, after
Product centrifugal purification is obtained into the cellulose (S-E-C) of the more sulfydryls of surface modification.
It step 4, is 1:17 by the mass ratio of the cellulose of the more sulfydryls of surface grafting and oxidant, by the more sulfydryls of surface grafting
Cellulose be immersed in oxidant, after mixing evenly, sealing, be placed at 90 DEG C and react 32 hours, generate cellulose base be grafted
Modified reversible gel.
Embodiment 5
Step 1, it weighs 0.5g (dry weight) cotton-shaped bacteria cellulose to be soaked in 80ml pyridine, ultrasonic disperse uniformly impregnates afterwards
It is centrifuged after 6 hours, repetitive operation obtains cellulose dispersion liquid three times.
Step 2, in the case where temperature is 50 DEG C of stirring conditions, by the glucoside unit and 10- undecene acyl chloride in cellulose
The molar ratio of reagent is 1:4, and 10- undecene acyl chloride reagent is slowly added in cellulose dispersion liquid, is kept the temperature under stirring condition
Reaction 8 hours, is transferred in alcoholic solvent after reaction, is centrifuged, repetitive operation obtains sediment, by sediment in tetrahydrofuran
Swelling, precipitating is centrifuged in ethanol, the cellulose (E-C) of terminal double bond in the surface modification that repetitive operation is purified；
Step 3, the cellulose of surface grafting terminal double bond and tetrahydrofuran are mixed to form to the suspension solution of 10mg/ml,
Molar ratio by glucoside unit and more mercapto reagents in cellulose is that TMMP is added into suspension by 1:8, is stirred at 25 DEG C,
And ultraviolet irradiation 4 hours, dialyse after reaction, change a solution within every 24 hours, change 2 times, after product is centrifuged
Purifying obtains the cellulose (S-E-C) of the more sulfydryls of surface modification.
Step 4, the cellulose of the more sulfydryls of surface grafting is immersed in and is configured to the suspension containing 35% cellulose in DMSO
Liquid, after mixing evenly, sealing are placed at 95 DEG C and react 12 hours, generate cellulose base graft modification reversible gel；
Fig. 2 is the cellulose base graft modification reversible gel prepared with this method；Fig. 3 is the table of this method step 3 preparation
The XPS spectrum figure of the cellulose of more sulfydryls is modified in face, and sulfydryl has successfully been modified up as seen from the figure.
Comparative example 1
This comparative example is substantially the same manner as Example 5, unique the difference is that the suspension concentration containing cellulose is in step 4
25%, it is placed at 95 DEG C and reacts 24 hours, generate cellulose base graft modification reversible gel.
Comparative example 2
This comparative example is substantially the same manner as Example 5, unique the difference is that the suspension concentration containing cellulose is in step 4
17%, it is placed at 95 DEG C and reacts 48 hours, generate cellulose base graft modification reversible gel；
Comparative example 3
This comparative example is substantially the same manner as Example 5, unique the difference is that the suspension concentration containing cellulose is in step 4
12%, it is placed at 95 DEG C and reacts 72 hours, generate cellulose base graft modification reversible gel；
Comparative example 1,2,3 is contrasted with embodiment 5, it can be found that content of cellulose is lower, the time required to forming gel
It is longer, and obtained gel hardness is poorer.
Embodiment 6
Reducing agent normal-temperature reaction 1~10 day will be added in cellulose base graft modification reversible gel made from each embodiment i.e.
Suspension can be all dissolved as, then thereto be added oxidant repeat step 4 can retrieve cellulose base graft modification can
Inverse gel.The reducing agent is selected from dithiothreitol (DTT) (DTT), 2 mercapto ethanol, three (2- carbonylethyl) microcosmic salt hydrochlorates
(TCEP) and it is without being limited thereto.
The redox reversible of this reversible description of test cellulose base graft modification reversible gel of the invention is can be with
It realizes.
Claims (8)
1. the preparation method of cellulose base graft modification reversible gel, which is characterized in that specific step is as follows:
Step 1, cellulose is soaked in organic solvent, after ultrasonic disperse is uniform, is impregnated 2~8 hours, centrifugation, repetitive operation
To remove impurity, cellulose dispersion liquid is obtained；
Step 2, at 25~80 DEG C, by cellulose glucoside unit and the molar ratio of the acid halide reagents containing terminal olefin be
1:1~12 are slowly added to the acid halide reagents containing terminal olefin in cellulose dispersion liquid, and insulation reaction 4 under stirring condition~
It 24 hours, is transferred in alcoholic solvent, is centrifuged, repetitive operation obtains sediment, and sediment is molten in swelling agent after reaction
It is swollen, centrifugation, the cellulose (E-C) for the surface grafting terminal double bond that repetitive operation is purified are precipitated in alcoholic solvent；
Step 3, the cellulose of surface grafting terminal double bond and swelling agent are mixed to form to the suspension of 5~40mg/ml, by fibre
The molar ratio of glucoside unit and more mercapto reagents in dimension element is 1:1~36, is added more mercapto reagents into suspension, 20~
It stirs at 40 DEG C, and ultraviolet irradiation 1~12 hour, dialyses after reaction, change a solution within every 12~24 hours, change 2
~4 times, after product centrifugal purification obtained into the cellulose (S-E-C) of the more sulfydryls of surface grafting；
It step 4, is 1:1~24 by the mass ratio of the cellulose of the more sulfydryls of surface grafting and oxidant, by the more sulfydryls of surface grafting
Cellulose be immersed in oxidant, after mixing evenly, sealing, react 6~120 hours, generate cellulose base graft modification can
Inverse gel.
2. preparation method according to claim 1, which is characterized in that in step 1, the cellulose can be natural fibre
Dimension element, synthetic cellulose, cellulose pattern can be cotton-shaped, membranaceous, whisker, powder.
3. preparation method according to claim 1, which is characterized in that in step 1, the cellulose is bacterial fibers
Element.
4. preparation method according to claim 1, which is characterized in that in step 1, the organic solvent be selected from pyridine,
Triethylamine, toluene or aniline.
5. preparation method according to claim 1, which is characterized in that in step 2, the carboxylic acid halides containing terminal olefin
The molecular formula of reagent is CH2=CH (CH2)1~10COX, X=Cl, Br, I, the alcoholic solvent is selected from methanol or ethyl alcohol, described
Swelling agent is selected from tetrahydrofuran or acetone.
6. preparation method according to claim 1, which is characterized in that in step 3, more mercapto reagents are selected from three hydroxyls
Methylpropane (3-thiopropionate), three-[3- mercaptopropionyl oxygroup-ethyl]-isocyanuric acid esters, (the 3- sulfydryl of pentaerythrite four
Propionic ester), diamyl antierythrite six (3-thiopropionate) or tetraethylene glycol it is bis- (3-thiopropionate).
7. preparation method according to claim 1, which is characterized in that in step 4, the oxidant be dimethyl sulfoxide or
When hydrogen peroxide, reaction temperature is 60~120 DEG C, and the oxidant is mixed selected from dimethyl sulfoxide or hydrogen peroxide and acid anhydrides
When conjunction, reaction temperature is 30~90 DEG C.
8. cellulose base graft modification reversible gel made from preparation method according to any one of claims 1 to 7.
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| CN115216063A (en) * | 2022-05-18 | 2022-10-21 | 苏州大学 | Cellulose graft modified hydrogel and preparation method thereof, medicinal cellulose hydrogel and application |
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