CN110408050B - Cellulose-based graft modified reversible gel and preparation method thereof - Google Patents

Cellulose-based graft modified reversible gel and preparation method thereof Download PDF

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CN110408050B
CN110408050B CN201810397543.XA CN201810397543A CN110408050B CN 110408050 B CN110408050 B CN 110408050B CN 201810397543 A CN201810397543 A CN 201810397543A CN 110408050 B CN110408050 B CN 110408050B
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CN110408050A (en
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孙东平
石琳
陈春涛
吕汶璐
林建斌
张威威
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Nanjing University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/005—Crosslinking of cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • 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
    • C08B3/10—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate with five or more carbon-atoms, e.g. valerate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives

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Abstract

The invention discloses a cellulose-based graft modified reversible gel and a preparation method thereof. The method comprises the steps of pretreating cellulose, adding the pretreated cellulose into an organic solvent to form a suspension, carrying out esterification reaction on the suspension, carrying out repeated centrifugal purification in the solvent to obtain modified cellulose with surface-modified terminal double bonds, then modifying the surface of the modified cellulose with multi-sulfydryl, and finally oxidizing the cellulose with the surface-modified multi-sulfydryl at the temperature of 30-120 ℃ for 6-120 hours to obtain the cellulose-based graft-modified reversible gel. The gel prepared by the invention can be changed into suspension under the action of a reducing agent and can be changed into gel again through oxidation. The raw material sources are safe and environment-friendly, the product has excellent biocompatibility, and the prepared gel has high mechanical strength and reversible performance, low toxicity and biocompatibility, and can be widely used in the fields of biological medicines, targeted drug sustained release, control of on-off reactors, recoverable soft materials and the like.

Description

Cellulose-based graft modified reversible gel and preparation method thereof
Technical Field
The invention relates to a gel with an organic matter as a matrix, in particular to a cellulose-based graft modified reversible gel and a preparation method thereof, belonging to the technical field of gel preparation.
Background
The gel is a polymer material with a three-dimensional network structure obtained by moderate crosslinking, has high solvent capacity and flexible natural characteristics, cannot be dissolved in a solvent, and has good biocompatibility. In addition, the gel has a porous structure and is very suitable for embedding substances with biological activity. The interaction force between the gel and the drug molecules is weak, and the controllable release of the gel to the drug is endowed by the regular swelling property while the activity of the drug is maintained. In addition, the gel has good structural controllability. Therefore, the gel as a novel medical biomaterial has wide application prospect in the fields of tissue engineering, drug delivery, controlled release and the like. In particular, the gel with stimulus responsiveness (such as pH, temperature and redox responsiveness) has great clinical application value.
Redox-responsive gels, the most representative of which is a gel containing disulfide bonds, are one of the hot spots studied in recent years. Disulfide bonds are widely found in humans, and one of the most important reactions in humans is the formation and cleavage of disulfide bonds. Under a reducing environment, disulfide bonds can be reduced to thiols; in an oxidizing environment, the two thiols can be oxidized to form disulfide bonds. Fairbanks et al (Fairbanks, B.D., et al.2011, Photogradeable, Photoadaptable Hydrogels via radio-Mediated degradation reaction. macromolecules 44(8): 2444-. Naga et al (Naga, Naofumi, Kazumasa Moriyama, and Hidimitusu Furukawa 2017Synthesis and properties of multifunctional thio crosslinked gels connecting complex bone in the network structure. journal of Polymer Science Part A: Polymer Chemistry 55(22):3749-3756.) Cross-linked gels containing disulfide bonds were obtained by oxidizing multi-thiol monomers in dimethyl sulfoxide. However, the gel prepared by the traditional method cannot simultaneously give consideration to excellent mechanical properties, good biocompatibility, degradability and feasibility of large-scale production.
Cellulose is a natural high polymer, is a macromolecular polysaccharide consisting of glucose, and is insoluble in water and common organic solvents. The crystal (nanocellulose, CNC) with the nano-size structure obtained by processing the cellulose has excellent mechanical property, high crystallinity, nano-size effect and good reproducibility and biodegradability. The nano-cellulose can improve the strength of the gel, but the enhancement effect of the mechanical property of the gel is limited only by directly filling and preparing the composite gel.
Disclosure of Invention
The invention aims to provide a cellulose-based graft modified reversible gel and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the cellulose-based graft modified reversible gel comprises the following specific steps:
step 1, soaking cellulose in an organic solvent, soaking for 2-8 hours after ultrasonic dispersion is uniform, centrifuging, and repeating the operation to remove impurities to obtain a cellulose dispersion liquid;
step 2, slowly adding the acyl halide reagent containing the terminal olefin into the cellulose dispersion liquid at the temperature of 25-80 ℃ according to the molar ratio of glucoside units in the cellulose to the acyl halide reagent containing the terminal olefin of 1: 1-12, carrying out heat preservation reaction for 4-24 hours under the stirring condition, transferring the mixture into an alcohol solvent after the reaction is finished, centrifuging, repeating the operation to obtain a precipitate, swelling the precipitate in a swelling reagent, precipitating and centrifuging in the alcohol solvent, and repeating the operation to obtain the purified cellulose (E-C) with the surface grafted with the terminal double bonds;
step 3, mixing the cellulose with the grafted terminal double bond on the surface and a swelling reagent to form 5-40 mg/ml suspension, adding a multi-sulfhydryl reagent into the suspension according to the molar ratio of glucoside units to the multi-sulfhydryl reagent in the cellulose being 1: 1-36, stirring at 20-40 ℃, carrying out ultraviolet irradiation for 1-12 hours, dialyzing after the reaction is finished, changing the solution once every 12-24 hours for 2-4 times, and carrying out centrifugal purification on the product after the reaction is finished to obtain the cellulose (S-E-C) with the grafted multi-sulfhydryl on the surface;
step 4, according to the mass ratio of the cellulose with the surface grafted with the multi-sulfydryl to the oxidant of 1: 1-24, immersing the cellulose with the surface grafted with the multi-sulfydryl into an oxidant, uniformly stirring, sealing, and reacting for 6-120 hours to generate the cellulose-based graft modified reversible gel.
In step 1, the cellulose may be natural cellulose, synthetic cellulose, or the like. The cellulose morphology can be flocculent, membranous, whisker, powder and the like. The cellulose may be bacterial cellulose, flocculent bacterial cellulose obtained by dynamic culture, membranous cellulose obtained by static culture, powder obtained by grinding the two, whisker obtained by hydrolysis and the like.
In step 1, the organic solvent is selected from pyridine, triethylamine, toluene or aniline, but is not limited thereto.
In step 2, the molecular formula of the acyl halide reagent containing the terminal olefin is CH2＝CH(CH2)1～10COX, X ═ Cl, Br, I, said alcoholic solvent is selected from methanol or ethanol, but not limited thereto, and said swelling agent is selected from tetrahydrofuran or acetone, but not limited thereto. The swelling agent and alcohol solvent used in the purification process are the same as those described above.
In step 3, the polymercapto reagent is selected from trimethylolpropane (3-mercaptopropionate) (TMMP), tris- [ 3-mercaptopropionyloxy-ethyl ] -isocyanurate (TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), dipentaerythritol hexa (3-mercaptopropionate) (DPMP), or tetraethyleneglycol bis (3-mercaptopropionate) (EGMP-4) and is not limited thereto.
In the step 4, when the oxidant is dimethyl sulfoxide (DMSO) or hydrogen peroxide, the reaction temperature is 60-120 ℃, and when the oxidant is selected from dimethyl sulfoxide (DMSO) or the mixture of hydrogen peroxide and anhydride, the reaction temperature is 30-90 ℃.
Compared with the prior art, the invention has the following advantages:
the method takes cellulose as a base material, grafts the polymer containing sulfhydryl groups on the surface of the cellulose, and oxidizes the cellulose to prepare the gel containing disulfide bonds and having a cross-linked network structure, the method has the advantages of easily obtained raw materials, safety and environmental protection, and the prepared gel has excellent mechanical properties, biocompatibility and redox reversibility, and can be widely used in the fields of biological medicines, targeted drug sustained release, control of switch reactors, recoverable soft materials and the like.
Drawings
FIG. 1 is a flow chart of a method for preparing a cellulose-based graft-modified reversible gel according to the present invention;
FIG. 2 is a physical diagram of a cellulose-based graft-modified reversible gel according to the present invention;
FIG. 3 is an XPS chart of the surface-modified polymercapto cellulose of the present invention.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
Step 1, weighing 0.8g (dry weight) of flocculent cellulose, soaking in 80ml of pyridine, soaking for 8 hours after uniform ultrasonic dispersion, centrifuging, and repeating the operation for three times to obtain a cellulose dispersion liquid.
And 2, under the condition of stirring at the temperature of 80 ℃, slowly adding the 10-undecylenoyl chloride reagent into the cellulose dispersion liquid according to the mol ratio of the glucoside unit to the 10-undecylenoyl chloride reagent of 1:1, keeping the temperature under the stirring condition for reaction for 4 hours, transferring the mixture into an alcohol solvent after the reaction is finished, centrifuging the mixture, repeating the operation to obtain a precipitate, swelling the precipitate in a swelling reagent, precipitating and centrifuging the precipitate in the alcohol solvent, and repeating the operation to obtain the purified cellulose (E-C) with the surface modified upper terminal double bond.
And 3, mixing the cellulose with the grafted terminal double bond on the surface and tetrahydrofuran to form a suspension solution of 5mg/ml, adding TMMP into the suspension solution according to the molar ratio of glucoside units in the cellulose to the multi-thiol reagent of 1:1, stirring at 40 ℃, carrying out ultraviolet irradiation for 12 hours, dialyzing after the reaction is finished, changing the solution once every 12 hours for 2 times, and carrying out centrifugal purification on the product after the reaction is finished to obtain the cellulose (S-E-C) with the modified multi-thiol surface.
Step 4, according to the mass ratio of the cellulose with the surface grafted with the multi-sulfydryl to the DMSO of 1:1, immersing the cellulose with the surface grafted with the multi-sulfhydryl group in DMSO, uniformly stirring, sealing, and reacting at 60 ℃ for 120 hours to generate the cellulose-based graft modified reversible gel.
Example 2
Step 1, weighing 1g of cellulose powder, adding the cellulose powder into 50ml of triethylamine, performing ultrasonic dispersion uniformly, soaking for 2 hours, centrifuging, and repeating the operation to remove redundant impurities to obtain cellulose dispersion liquid.
And 2, under the condition of stirring at the temperature of 25 ℃, slowly adding 10-undecylenoyl chloride into the cellulose dispersion liquid according to the molar ratio of glucoside units to 10-undecylenoyl chloride of 1:12, keeping the temperature under the stirring condition for reaction for 24 hours, transferring the mixture into an alcohol solvent after the reaction is finished, centrifuging the mixture, repeating the operation to obtain a precipitate, swelling the precipitate in acetone, precipitating the precipitate in methanol and centrifuging the precipitate, and repeating the operation to obtain the purified cellulose (E-C) with the double bonds at the upper end of the surface modification.
And 3, mixing the cellulose with the grafted terminal double bond on the surface and acetone to form a suspension solution of 40mg/ml, adding TEMPIC into the suspension according to the molar ratio of glucoside units in the cellulose to the multi-thiol reagent of 1:36, stirring at 20 ℃, carrying out ultraviolet irradiation for 1 hour, dialyzing after the reaction is finished, changing the solution once every 24 hours, changing for 4 times, and carrying out centrifugal purification on the product after the reaction is finished to obtain the cellulose (S-E-C) with the modified multi-thiol surface.
Step 4, according to the mass ratio of the cellulose with the surface grafted with the multi-sulfydryl to the DMSO of 1: 24, immersing the cellulose with the surface grafted with the multi-sulfhydryl group in DMSO, uniformly stirring, sealing, and reacting at 120 ℃ for 6 hours to generate cellulose-based graft modified reversible gel;
example 3
Step 1, weighing 0.5g of cellulose whiskers, adding the cellulose whiskers into 50ml of triethylamine, performing ultrasonic dispersion uniformly, soaking for 6 hours, centrifuging, and repeating the operation to remove redundant impurities to obtain a cellulose dispersion solution;
step 2, under the condition of stirring at the temperature of 50 ℃, slowly adding 10-undecylenoyl chloride into cellulose dispersion liquid according to the molar ratio of glucoside units to 10-undecylenoyl chloride of 1:8, keeping the temperature for reaction for 7 hours under the condition of stirring, transferring the mixture into an alcohol solvent after the reaction is finished, centrifuging the mixture, repeating the operation to obtain a precipitate, swelling the precipitate in acetone, precipitating and centrifuging the precipitate in methanol, repeating the operation to obtain purified cellulose (E-C) with double bonds at the upper end of the surface modification,
and 3, mixing the cellulose with the grafted terminal double bond on the surface and acetone to form a suspension solution of 20mg/ml, adding PEMP into the suspension solution according to the molar ratio of glucoside units in the cellulose to the multi-thiol reagent of 1:2, stirring at 25 ℃, carrying out ultraviolet irradiation for 3 hours, dialyzing after the reaction is finished, changing the solution once every 12 hours for 4 times, and carrying out centrifugal purification on the product after the reaction is finished to obtain the cellulose (S-E-C) with the modified multi-thiol surface.
Step 4, according to the mass ratio of the cellulose with the surface grafted with the multi-sulfydryl to the DMSO of 1: 10, immersing the cellulose with the surface grafted with the multi-sulfhydryl group in DMSO, uniformly stirring, sealing, and reacting at 120 ℃ for 16 hours to generate cellulose-based graft modified reversible gel;
example 4
Step 1, weighing 0.5g of crushed cellulose, soaking the crushed cellulose in aniline, performing ultrasonic dispersion uniformly, soaking the crushed cellulose for 4 hours, centrifuging the soaked cellulose, and repeating the operation to remove redundant impurities to obtain cellulose dispersion liquid.
And 2, under the condition of stirring at the temperature of 60 ℃, slowly adding 10-undecylenoyl chloride into the cellulose dispersion liquid according to the molar ratio of glucoside units to 10-undecylenoyl chloride reagent of 1:8, keeping the temperature for reaction for 7 hours under the stirring condition, transferring the mixture into an alcohol solvent after the reaction is finished, centrifuging the mixture, repeating the operation to obtain a precipitate, swelling the precipitate in a swelling reagent, precipitating and centrifuging the precipitate in the alcohol solvent, and repeating the operation to obtain the purified cellulose (E-C) with the surface modified upper terminal double bond.
And 3, mixing the cellulose with the grafted terminal double bond on the surface and a swelling reagent to form a suspension solution of 15mg/ml, adding a reagent containing the multi-sulfhydryl into the suspension solution according to the molar ratio of glucoside units to the multi-sulfhydryl reagent of 1:8, stirring at 30 ℃, carrying out ultraviolet irradiation for 5 hours, dialyzing after the reaction is finished, changing the solution once every 16 hours, changing for 3 times, and carrying out centrifugal purification on the product after the reaction is finished to obtain the cellulose (S-E-C) with the modified multi-sulfhydryl on the surface.
Step 4, according to the mass ratio of the cellulose with the surface grafted with the multi-sulfydryl to the oxidant of 1: and 17, immersing the cellulose with the surface grafted with the multi-sulfhydryl group into an oxidant, uniformly stirring, sealing, and reacting at 90 ℃ for 32 hours to generate the cellulose-based graft modified reversible gel.
Example 5
Step 1, weighing 0.5g (dry weight) of flocculent bacterial cellulose, soaking in 80ml of pyridine, carrying out ultrasonic dispersion uniformly, soaking for 6 hours, centrifuging, and repeating the operation for three times to obtain a cellulose dispersion liquid.
Step 2, under the condition of stirring at the temperature of 50 ℃, slowly adding a 10-undecylenoyl chloride reagent into a cellulose dispersion liquid according to the molar ratio of a glucoside unit to the 10-undecylenoyl chloride reagent of 1:4, keeping the temperature under the condition of stirring for reaction for 8 hours, transferring the mixture into an alcohol solvent after the reaction is finished, centrifuging the mixture, repeating the operation to obtain a precipitate, swelling the precipitate in tetrahydrofuran, precipitating and centrifuging the precipitate in ethanol, and repeating the operation to obtain purified cellulose (E-C) with a surface modified upper terminal double bond;
and 3, mixing the cellulose with the grafted terminal double bond on the surface and tetrahydrofuran to form a suspension solution of 10mg/ml, adding TMMP into the suspension solution according to the molar ratio of glucoside units in the cellulose to the multi-thiol reagent of 1:8, stirring at 25 ℃, carrying out ultraviolet irradiation for 4 hours, dialyzing after the reaction is finished, changing the solution once every 24 hours, changing for 2 times, and carrying out centrifugal purification on the product after the reaction is finished to obtain the cellulose (S-E-C) with the modified multi-thiol surface.
Step 4, immersing the cellulose with the surface grafted with the multi-sulfydryl into DMSO (dimethyl sulfoxide) to prepare a suspension containing 35% of cellulose, uniformly stirring, sealing, and reacting at 95 ℃ for 12 hours to generate cellulose-based graft modified reversible gel;
FIG. 2 is a cellulose-based graft-modified reversible gel prepared by the present method; FIG. 3 is an XPS spectrum of the surface-modified multi-thiol cellulose prepared in step 3 of the method, and it can be seen that thiol groups are successfully modified.
Comparative example 1
This comparative example is essentially the same as example 5, except that the cellulose-containing suspension of step 4, having a concentration of 25%, is allowed to react at 95 ℃ for 24 hours to form a cellulose-based graft-modified reversible gel.
Comparative example 2
This comparative example is essentially the same as example 5, except that the concentration of the cellulose-containing suspension in step 4 is 17%, and the reaction is carried out at 95 ℃ for 48 hours to produce a cellulose-based graft-modified reversible gel;
comparative example 3
This comparative example is essentially the same as example 5, except that the concentration of the cellulose-containing suspension in step 4 is 12%, and the reaction is carried out at 95 ℃ for 72 hours to produce a cellulose-based graft-modified reversible gel;
comparative examples 1, 2, 3 in contrast to example 5, it was found that the lower the cellulose content, the longer the time required to form the gel and the poorer the hardness of the gel obtained.
Example 6
And (3) adding a reducing agent into the cellulose-based graft-modified reversible gel prepared in each embodiment, reacting at normal temperature for 1-10 days to completely dissolve the gel into a suspension, adding an oxidizing agent into the suspension, and repeating the step (4) to obtain the cellulose-based graft-modified reversible gel again. The reducing agent is selected from Dithiothreitol (DTT), 2-mercaptoethanol, tris (2-carbonylethyl) phosphate (TCEP) and is not limited thereto.
This reversible experiment demonstrates that the redox reversibility of the cellulose-based graft-modified reversible gel of the present invention is achievable.

Claims (7)

1. The preparation method of the cellulose-based graft modified reversible gel is characterized by comprising the following specific steps:
step 1, soaking cellulose in an organic solvent, soaking for 2-8 hours after ultrasonic dispersion is uniform, centrifuging, and repeating the operation to remove impurities to obtain a cellulose dispersion liquid;
step 2, slowly adding the acyl halide reagent containing the terminal olefin into cellulose dispersion liquid at the temperature of 25-80 ℃ according to the molar ratio of a glucoside unit in the cellulose to the acyl halide reagent containing the terminal olefin of 1: 1-12, carrying out heat preservation reaction for 4-24 hours under the stirring condition, transferring the mixture into an alcohol solvent after the reaction is finished, centrifuging, repeating the operation to obtain a precipitate, swelling the precipitate in a swelling reagent, precipitating and centrifuging in the alcohol solvent, and repeating the operation to obtain the purified cellulose with the surface grafted with the terminal double bond, wherein the swelling reagent is selected from tetrahydrofuran or acetone;
step 3, mixing the cellulose with the grafted terminal double bond on the surface and a swelling reagent to form 5-40 mg/ml suspension, adding a multi-sulfhydryl reagent into the suspension according to the molar ratio of glucoside units to the multi-sulfhydryl reagent in the cellulose being 1: 1-36, stirring at 20-40 ℃, carrying out ultraviolet irradiation for 1-12 hours, dialyzing after the reaction is finished, changing the solution once every 12-24 hours, changing for 2-4 times, and carrying out centrifugal purification on the product after the reaction is finished to obtain the cellulose with the grafted multi-sulfhydryl on the surface;
step 4, according to the mass ratio of the cellulose with the surface grafted with the multi-sulfydryl to the oxidant of 1: 1-24, immersing cellulose with the surface grafted with the multi-sulfydryl in an oxidant, uniformly stirring, sealing, and reacting for 6-120 hours to generate the cellulose-based graft modified reversible gel, wherein when the oxidant is dimethyl sulfoxide or hydrogen peroxide, the reaction temperature is 60-120 ℃, and when the oxidant is selected from dimethyl sulfoxide or hydrogen peroxide and anhydride, the reaction temperature is 30-90 ℃.
2. The method according to claim 1, wherein in step 1, the cellulose is natural cellulose or synthetic cellulose, and the cellulose is flocculent, film-like, whisker or powder.
3. The method according to claim 1, wherein in step 1, the cellulose is bacterial cellulose.
4. The method according to claim 1, wherein in step 1, the organic solvent is selected from pyridine, triethylamine, toluene, and aniline.
5. The method of claim 1, wherein in step 2, the terminal olefin-containing acid halide reagent has the formula CH2＝CH(CH2)1～10COX, X ═ Cl, Br, I, and the alcohol solvent is selected from methanol or ethanol.
6. The method of claim 1, wherein in step 3, said polymercapto reagent is selected from trimethylolpropane tris (3-mercaptopropionate), tris- [ 3-mercaptopropionyloxy-ethyl ] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and tetraethyleneglycol bis (3-mercaptopropionate).
7. The cellulose-based graft-modified reversible gel prepared according to the preparation method of any one of claims 1 to 6.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101200504A (en) * 2006-12-11 2008-06-18 上海百瑞吉生物医药有限公司 Macromolecule thiolated modified derivatives and cross-linking material thereof
WO2012057751A1 (en) * 2010-10-27 2012-05-03 Empire Technology Development Llc Crosslinked cellulosic polymers
CN105039465A (en) * 2015-07-28 2015-11-11 南昌大学 Enzyme-catalyzed disulfide bond-crosslinked natural polymer hydrogel and preparation method thereof
CN106893118A (en) * 2017-03-24 2017-06-27 东华大学 A kind of pH and redox double-response polysaccharide hydrogel and its preparation and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101200504A (en) * 2006-12-11 2008-06-18 上海百瑞吉生物医药有限公司 Macromolecule thiolated modified derivatives and cross-linking material thereof
WO2012057751A1 (en) * 2010-10-27 2012-05-03 Empire Technology Development Llc Crosslinked cellulosic polymers
CN105039465A (en) * 2015-07-28 2015-11-11 南昌大学 Enzyme-catalyzed disulfide bond-crosslinked natural polymer hydrogel and preparation method thereof
CN106893118A (en) * 2017-03-24 2017-06-27 东华大学 A kind of pH and redox double-response polysaccharide hydrogel and its preparation and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Amination and thiolation of chloroacetyl cellulose through reactive dissolution in N,N-dimethylformamide";Sara R. Labafzadeh等;《Carbohydrate Polymers》;20140402;第116卷;60-66 *
"Highly efficient and straightforward functionalization of cellulose films with thiol-ene click chemistry";Philippe Tingaut等;《J. Mater. Chem.》;20111231;第21卷;16066-16076 *

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