CN106750382A - A kind of preparation method of chitosan gel rubber pearl - Google Patents
A kind of preparation method of chitosan gel rubber pearl Download PDFInfo
- Publication number
- CN106750382A CN106750382A CN201611176504.4A CN201611176504A CN106750382A CN 106750382 A CN106750382 A CN 106750382A CN 201611176504 A CN201611176504 A CN 201611176504A CN 106750382 A CN106750382 A CN 106750382A
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- CN
- China
- Prior art keywords
- gel rubber
- shitosan
- sodium
- solution
- chitosan gel
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 36
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000002775 capsule Substances 0.000 claims abstract description 25
- 230000000694 effects Effects 0.000 claims abstract description 24
- 239000000975 dye Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 150000003384 small molecules Chemical class 0.000 claims abstract description 11
- -1 sodium glycero-phosphate pentahydrate Chemical class 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 239000005457 ice water Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- DHCLVCXQIBBOPH-UHFFFAOYSA-N β-glycerophosphoric acid Chemical compound OCC(CO)OP(O)(O)=O DHCLVCXQIBBOPH-UHFFFAOYSA-N 0.000 claims description 27
- AVPCPPOOQICIRJ-UHFFFAOYSA-L disodium;1,3-dihydroxypropan-2-yl phosphate Chemical compound [Na+].[Na+].OCC(CO)OP([O-])([O-])=O AVPCPPOOQICIRJ-UHFFFAOYSA-L 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 14
- 239000011324 bead Substances 0.000 claims description 11
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- 239000003094 microcapsule Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 238000003381 deacetylation reaction Methods 0.000 claims description 5
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 5
- 235000019800 disodium phosphate Nutrition 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001105 regulatory Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M Monopotassium phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000004676 glycans Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 150000004804 polysaccharides Polymers 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- 229960002901 Sodium glycerophosphate Drugs 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001879 gelation Methods 0.000 abstract description 2
- 239000008236 heating water Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 6
- 229940020947 fluorescein sodium Drugs 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 229920002101 Chitin Polymers 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- DJHJJVWPFGHIPH-OODMECLYSA-N Chitin Chemical compound O[C@@H]1C(NC(=O)C)[C@H](O)OC(CO)[C@H]1COC[C@H]1C(NC(C)=O)[C@@H](O)[C@H](COC[C@H]2C([C@@H](O)[C@H](O)C(CO)O2)NC(C)=O)C(CO)O1 DJHJJVWPFGHIPH-OODMECLYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N Rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 Rhodamine B Drugs 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- OFNNKPAERNWEDD-UHFFFAOYSA-L disodium;2,3-dihydroxypropyl phosphate;hydrate Chemical compound O.[Na+].[Na+].OCC(O)COP([O-])([O-])=O OFNNKPAERNWEDD-UHFFFAOYSA-L 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- LOMHJEGAUNMOOE-ZXXMMSQZSA-N (2R,3S,4R,5R)-2-amino-2,3,4,5,6-pentahydroxyhexanal Chemical compound O=C[C@@](O)(N)[C@@H](O)[C@H](O)[C@H](O)CO LOMHJEGAUNMOOE-ZXXMMSQZSA-N 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L Congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L Dipotassium phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 108010054033 EC 3.5.1.41 Proteins 0.000 description 1
- 229960002442 Glucosamine Drugs 0.000 description 1
- CMHHMUWAYWTMGS-UHFFFAOYSA-N Oxybuprocaine Chemical compound CCCCOC1=CC(C(=O)OCCN(CC)CC)=CC=C1N CMHHMUWAYWTMGS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QNWKDKZDODZBCV-UHFFFAOYSA-N sodium;pentahydrate Chemical compound O.O.O.O.O.[Na+] QNWKDKZDODZBCV-UHFFFAOYSA-N 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention discloses a kind of capsule shape and the preparation method of the chitosan gel rubber pearl that can contain small molecule dyes, belong to chitosan gel rubber pearl fabricating technology field.The preparation method is：Shitosan is dissolved in acetum, and β sodium glycero-phosphate pentahydrate solution is slowly added dropwise in ice-water bath.And adjust mixed solution pH value to neutrality.The shitosan that will be prepared/β sodium glycero-phosphate pentahydrates mixed solution (CS/ β GP solution) is instilled in SDS reception liquids, and the shitosan drop of parcel CS/ β GP solution is formed after curing.After heating water bath, there is gelation in the internal effect due to hydrogen bond, finally give chitosan gel rubber pearl.The small molecule dyes of chitosan gel rubber pearl prepared by the present invention to molecular weight between 300 800 have excellent containing property, and dye leakage amount is few, contains good stability, still without substantially leakage after 12h.
Description
Technical field
The invention belongs to chitosan gel rubber pearl preparation technology field, particularly a kind of capsule shape and small molecule dyes can be contained
Chitosan gel rubber pearl preparation method.
Technical background
Shitosan (chitosan, CS) is white or canescence, slightly has pearly luster, translucent chip solid, also known as de-
Acetyl chitin, soluble chitin, poly glucosamine, are the products of chitin deacetylase base.The average molecular of shitosan
From hundreds thousand of to millions of, molecular formula is (C to quality6HllO4N) n, monomer is generally 2- amino-D-Glucose.Shitosan
Solubility property is better than chitin, dissolves in dilute organic acid and part inorganic acid, such as lactic acid, hydrochloric acid and acetic acid, but do not dissolve in
Dilute sulfuric acid, dust technology, phosphoric acid,diluted, oxalic acid, water insoluble and aqueous slkali, low viscous shitosan even can be dissolved in water.
N- deacetylations and viscosity (can reflect average molecular mass) are two main character indexs of shitosan.One
As for, the chitin of deacetylation (deacetylation degree, DD) more than 50% is referred to as shitosan, deacetylated
Degree is higher, and the amino rate of ionization in chitosan molecule chain is higher, more soluble in water.According to the difference of viscosity, can be
Shitosan is divided into three kinds.The 1% shitosan acetic acid solution generally viscosity in more than 1000cps calls high-viscosity chitosan, glues
Spend and be referred to as middle viscosity shitosan in 100~1000cps, be bonded at below 100cps is referred to as low viscosity shitosan.Other conditions
In the case of identical, the viscosity of shitosan is bigger, and the solubility in water is smaller.
Shitosan-sodium glycero-phosphate thermo-sensitive gel system sees 2000 earliest, once proposition, that is, is paid high attention to.
First it is that the system uses natural macromolecular material shitosan, its biocompatibility is gradually ground with biodegradability
The accreditation of the person of studying carefully.In addition, simple shitosan only keeps solution state under sour environment, when pH value is increased to 6.9-7.1,
Chitosan solution starts precipitation occur, but in the presence of weak base sodium glycero-phosphate, the system can in neutral conditions keep stabilization
Solution state, this is that the protein-based medicine of system loads cell even living is provided convenience condition.It is finally that this is
System has temperature-sensing property, is in solution state below room temperature, and temperature is increased to curable formation gel during body temperature, such that it is able to slow
Release the effect of loading medicine.If but being loaded directly into protein-based medicine with shitosan-sodium glycero-phosphate thermo-sensitive gel system
Still there is some in cell even living：
1. the form of gel does not know.
2., due to the unclosed property of gel, containing the small molecules such as medicine dyestuff inside gel may in transmittance process
Gel can be departed from.
3. to contain medicine mechanical strength very poor for single gel, contains structure and is easily destroyed.
Some problem for more than, the present invention develops a kind of with closure and the certain capsule shape gel beads of form.
The content of the invention
The technical problems to be solved by the invention are：The shitosan for providing a kind of capsule shape and can containing small molecule dyes coagulates
The preparation method of glue bead.The stability that contains of dyestuff is improved by the structure design of microcapsule coated microgel, leakage is reduced
Amount.
The present invention solves its technical problem and uses following technical scheme：
The preparation method of the chitosan gel rubber pearl that the present invention is provided, specifically：First by shitosan and sodium β-glycerophosphate
Mixed solution by liquid-transfering gun, be added drop-wise in anionic surfactant solution, based on shitosan and anion surface active
The cohesion of agent, forms the chitosan capsules that core also has shitosan and sodium β-glycerophosphate；Then, by heating, glue is made
The shitosan and sodium β-glycerophosphate in intracapsular portion form gel by hydrogen bond action, finally give chitosan gel rubber pearl.
The preparation method of described chitosan gel rubber pearl, comprises the following steps：
(1) preparation of shitosan/sodium β-glycerophosphate pentahydrate mixed solution：
1.2g-1.6g sodium β-glycerophosphate pentahydrates are dissolved in 2mL water, and the middle viscosity shitosan of 0.4g is molten
Solution is in the acetum of 0.1mol/L；Under ice-water bath, to being slowly added dropwise β-phosphoglycerol in the chitosan solution for having dissolved
Sodium pentahydrate solution, obtains shitosan/sodium β-glycerophosphate pentahydrate mixed solution, and it is molten that it is referred to as CS/ β-GP mixing
Liquid；
(2) regulation of shitosan/sodium β-glycerophosphate pentahydrate mixed solution pH value and sodium dodecyl sulfate solution
Preparation：
Weigh 25g disodium hydrogen phosphate solids to be dissolved in 100ml water, dissolving obtains the disodium phosphate soln of saturation；To CS/
The disodium phosphate soln of β-GP mixed solution and dripping saturations adjusts pH value between 6.9-7.1；Weigh 0.2g-0.8 12
Sodium alkyl sulfate solid is dissolved in 20mL water, prepares the lauryl sodium sulfate reception liquid of mass fraction 1%-4%, and it is referred to as
SDS reception liquids；
(3) preparation of chitosan gel rubber pearl：
To be regulated during CS/ β-GP solution that pH value is 6.9-7.1 instills SDS reception liquids with liquid-transfering gun, obtained after curing
Chitosan microcapsules, then with water washing is distilled 3 times, place into heating in water-bath, and the CS/ β-GP solution inside microcapsules turns
It is changed into gel, so as to obtain chitosan gel rubber pearl.
In the above method, described middle viscosity shitosan, its viscosity is 200-400mPa.s, deacetylation >=90%.
In the above method, can be by CS/ β-GP solution instillation SDS reception liquids, its curing time is 50-70min.
In the above method, it is possible to use weakly alkaline solution adjusts the pH value of CS/ β-GP solution, the weakly alkaline solution uses phosphorus
Sour disodium hydrogen or potassium dihydrogen phosphate.
In the above method, when chitosan microcapsules are changed into gel beads, bath temperature is 39-45 DEG C, and water bath time is 4-
7min。
In the above method, the mass ratio of shitosan and sodium β-glycerophosphate is 1/3-1/4.
Chitosan gel rubber pearl prepared by the above method that the present invention is provided, its application in small molecule dyes are contained.
When the chitosan gel rubber pearl is applied, its small molecule dyes to molecular weight between 350-800 has excellent containing
Property, 12 hours are placed without substantially leakage, contain stability with good.
The present invention has following main beneficial effect compared with prior art：
1. CS/GP mixed solutions can be directly instilled in SDS acceptable solutions and obtain gel beads in heating water bath, internal gel with
Outside clad structure one-shot forming, without following process, reduces manufacture difficulty, improves producing efficiency.
2. the chitosan gel rubber ball for preparing can be applied to the cladding of small molecule dyes.The molecular weight for containing dyestuff exists
Between 300-800, dye leakage amount is few, contains good stability, still without substantially leakage after 12h.
3. the gel beads for preparing are respectively provided with the excellent effect that contains to various dyestuffs, such as to fluorescein sodium (molecule
Measure for 376), rhodamine B (molecular weight is 479), Congo red (molecular weight is 697) etc. have preferably parcel effect.
4. the gel beads for preparing can more intuitively be observed and contained inside gel beads dye due to the high transparency of its own
Expect the leak case of dyestuff, will not due to the Color influences of gel beads itself observing effect.For example contain fluorescence by what is prepared
The gel beads of plain sodium dyestuff are immersed in the aqueous solution of 50ml, are stood overnight at ambient temperature, and research is coated in gel ball
The leak case of the fluorescein sodium in portion.As shown in figure 1, the chitosan gel rubber pearl after temperature-induced gelation, has to fluorescein sodium
There is preferable covered effect, and effectively reduce fluorescein sodium leakage in aqueous in chitosan gel rubber pearl.
Brief description of the drawings
Fig. 1 is the inside SEM figures of chitosan microcapsules.
Fig. 2 is the inside SEM figures of temperature-induced rear shitosan/sodium glycero-phosphate composite micro-capsule.
Fig. 3 is that the chitosan gel rubber pearl for having coated fluorescein sodium places the shape appearance figure of 12h in water.
Specific embodiment
With reference to embodiment and accompanying drawing, the invention will be further described, and it is right that certain following embodiments should not be construed as
Limitation of the invention.
1. the preparation method of the chitosan gel rubber pearl of a kind of capsule shape：
Embodiment 1：
1.4g sodium β-glycerophosphate pentahydrates are dissolved in 2mL water, and are 200-400mPa.s's by 0.4g viscosity
Middle viscosity shitosan is dissolved in the acetum of 0.1mol/L.Accelerating stirring makes its quick dissolving.Being stood after dissolving gathers shell
Bubble in sugar juice sheds completely.Weigh 25g disodium hydrogen phosphate solids to be dissolved in 100ml water, obtain the phosphoric acid hydrogen two of saturation
Sodium solution.Under ice-water bath, to sodium β-glycerophosphate pentahydrate solution is slowly added dropwise in the chitosan solution for having dissolved, it is added dropwise
After the completion of, adjust pH value with the disodium phosphate soln of saturation and mixed to shitosan/sodium β-glycerophosphate between 6.9-7.1, is obtained
Close solution (CS/ β-GP mixed solutions).Weigh 0.2g-0.8g lauryl sodium sulfate solids to be dissolved in 20mL water, prepare quality
The sodium dodecyl sulfate solution of fraction 2% is used as reception liquid.With liquid-transfering gun by CS/ β-GP mixed solutions instill reception liquid in,
Curing can form translucent white globules in 1 hour.With water washing bead is distilled 3 times, insulation in 42 DEG C of water-baths is placed into
5min, you can obtain the chitosan gel rubber pearl of capsule shape.
Embodiment 2：
It is formulated according to embodiment 1, the change curing time is 50min, its condition is constant.It is prepared by the step of according to embodiment 1
The chitosan gel rubber pearl of the capsule shape that present case is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, and middle viscosity shell gathers
The consumption of sugar is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is regulation pH value
0.2g, bath temperature is 42 DEG C, and water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 3：
It is formulated according to embodiment 1, the change curing time is 60min, its condition is constant.It is prepared by the step of according to embodiment 1
The chitosan gel rubber pearl of the capsule shape that present case is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, and middle viscosity shell gathers
The consumption of sugar is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is regulation pH value
0.2g, bath temperature is 42 DEG C, and water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 4：
It is formulated according to embodiment 1, the change curing time is 70min, its condition is constant.It is prepared by the step of according to embodiment 1
The chitosan gel rubber pearl of the capsule shape that present case is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, and middle viscosity shell gathers
The consumption of sugar is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is regulation pH value
0.2g, bath temperature is 42 DEG C, and water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 5：
It is formulated according to embodiment 1, bath temperature is changed to 39 DEG C, its condition is constant.The step of according to embodiment 1, prepares this case
The chitosan gel rubber pearl of the capsule shape that example is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, middle viscosity shitosan
Consumption is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value,
Curing time is 1h, and water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 6：
It is formulated according to embodiment 1, bath temperature is changed to 42 DEG C, its condition is constant.The step of according to embodiment 1, prepares this case
The chitosan gel rubber pearl of the capsule shape that example is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, middle viscosity shitosan
Consumption is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value,
Curing time is 1h, and water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 7：
It is formulated according to embodiment 1, bath temperature is changed to 45 DEG C, its condition is constant.The step of according to embodiment 1, prepares this case
The chitosan gel rubber pearl of the capsule shape that example is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, middle viscosity shitosan
Consumption is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value,
Curing time is 1h, and water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 8：
It is formulated according to embodiment 1, water bath time is changed to 4min, its condition is constant.The step of according to embodiment 1, prepares this case
The chitosan gel rubber pearl of the capsule shape that example is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, middle viscosity shitosan
Consumption is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value,
Curing time is 1h, and bath temperature is 42 DEG C.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 9：
It is formulated according to embodiment 1, water bath time is changed to 7min, its condition is constant.The step of according to embodiment 1, prepares this case
The chitosan gel rubber pearl of the capsule shape that example is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, middle viscosity shitosan
Consumption is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value,
Curing time is 1h, and bath temperature is 42 DEG C.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 10：
It is formulated according to embodiment 1, water bath time is changed to 7min, its condition is constant.The step of according to embodiment 1, prepares this case
The chitosan gel rubber pearl of the capsule shape that example is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, middle viscosity shitosan
Consumption is 0.4g, and acetate concentration is 0.1mol/L, and between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value,
Curing time is 1h, and bath temperature is 42 DEG C.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 11：
It is formulated according to embodiment 1, pH adjusting agent is changed to dipotassium hydrogen phosphate, its condition is constant.The step of according to embodiment 1
Prepare the chitosan gel rubber pearl of the capsule shape that present case is implemented.The consumption of sodium β-glycerophosphate pentahydrate is 1.4g, middle viscosity
The consumption of shitosan is 0.4g, and acetate concentration is 0.1mol/L, and regulation pH value between 6.9-7.1, use by lauryl sodium sulfate
It is 0.2g to measure, and the curing time is 1h, and bath temperature is 42 DEG C, and water bath time is 5min.Also can obtain the excellent shell of gel effect
Polysaccharide gel pearl.
Embodiment 12：
It is formulated according to embodiment 1, it is 1.6g to change sodium β-glycerophosphate quality, and its condition is constant.According to the step of embodiment 1
The rapid chitosan gel rubber pearl for preparing the capsule shape that present case is implemented.The consumption of middle viscosity shitosan is 0.4g, and acetate concentration is
0.1mol/L, between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value, and the curing time is 1h, bath temperature
It it is 42 DEG C, water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 13：
It is formulated according to embodiment 1, it is 1.4g to change sodium β-glycerophosphate quality, and its condition is constant.According to the step of embodiment 1
The rapid chitosan gel rubber pearl for preparing the capsule shape that present case is implemented.The consumption of middle viscosity shitosan is 0.4g, and acetate concentration is
0.1mol/L, between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value, and the curing time is 1h, bath temperature
It it is 42 DEG C, water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 14：
It is formulated according to embodiment 1, it is 1.2g to change sodium β-glycerophosphate quality, and its condition is constant.According to the step of embodiment 1
The rapid chitosan gel rubber pearl for preparing the capsule shape that present case is implemented.The consumption of middle viscosity shitosan is 0.4g, and acetate concentration is
0.1mol/L, between 6.9-7.1, lauryl sodium sulfate consumption is 0.2g to regulation pH value, and the curing time is 1h, bath temperature
It it is 42 DEG C, water bath time is 5min.Also can obtain the excellent chitosan gel rubber pearl of gel effect.
Embodiment 15：
It is formulated according to embodiment 1, it is 1% to change SDS reception liquids mass fraction, and its condition is constant.According to the step of embodiment 1
The rapid chitosan gel rubber pearl for preparing the capsule shape that present case is implemented.The consumption of sodium β-glycerophosphate pentahydrate be 1.4g, in glue
Spend shitosan consumption be 0.4g, acetate concentration is 0.1mol/L, regulation pH value between 6.9-7.1, lauryl sodium sulfate
Consumption is 0.2g, and the curing time is 1h, and bath temperature is 42 DEG C, and water bath time is 5min.Also can obtain gel effect excellent
Chitosan gel rubber pearl.
Embodiment 16：
It is formulated according to embodiment 1, it is 2% to change SDS reception liquids mass fraction, and its condition is constant.According to the step of embodiment 1
The rapid chitosan gel rubber pearl for preparing the capsule shape that present case is implemented.The consumption of sodium β-glycerophosphate pentahydrate be 1.4g, in glue
Spend shitosan consumption be 0.4g, acetate concentration is 0.1mol/L, regulation pH value between 6.9-7.1, lauryl sodium sulfate
Consumption is 0.8g, and the curing time is 1h, and bath temperature is 42 DEG C, and water bath time is 5min.Also can obtain gel effect excellent
Chitosan gel rubber pearl.
Embodiment 17：
It is formulated according to embodiment 1, it is 4% to change SDS reception liquids mass fraction, and its condition is constant.According to the step of embodiment 1
The rapid chitosan gel rubber pearl for preparing the capsule shape that present case is implemented.The consumption of sodium β-glycerophosphate pentahydrate be 1.4g, in glue
Spend shitosan consumption be 0.4g, acetate concentration is 0.1mol/L, regulation pH value between 6.9-7.1, lauryl sodium sulfate
Consumption is 0.8g, and the curing time is 1h, and bath temperature is 42 DEG C, and water bath time is 5min.Also can obtain gel effect excellent
Chitosan gel rubber pearl.
2. chitosan gel rubber pearl contains the preparation method of small molecule：
Embodiment 18：
Regulated in Example 1 pH value shitosan/(CS/ β-GP are molten for sodium β-glycerophosphate pentahydrate mixed solution
Liquid), it is the Fluress of 1mg/L that 1mL mass fractions are added dropwise thereto.After stirring is completely dispersed it, remaining prepares step
It is rapid in the same manner as in Example 1.The chitosan gel rubber pearl that fluorescein sodium will have been coated is placed 12 hours in water, without substantially leakage,
Contain and work well, as shown in Figure 2.
Embodiment 19：
Regulated in Example 1 pH value shitosan/(CS/ β-GP are molten for sodium β-glycerophosphate pentahydrate mixed solution
Liquid), it is the rhodamine B solution of 1mg/L that 1mL mass fractions are added dropwise thereto.After stirring is completely dispersed it, remaining preparation process
It is in the same manner as in Example 1.Revealed without obvious after placing 12h, contain and work well.
Claims (9)
1. a kind of preparation method of chitosan gel rubber pearl, it is characterised in that：First by the mixing of shitosan and sodium β-glycerophosphate
Solution is added drop-wise in anionic surfactant solution by liquid-transfering gun, solidifying with anion surfactant based on shitosan
Poly- effect, forms the chitosan capsules that core also has shitosan and sodium β-glycerophosphate；Then, by heating, capsule is made
Shitosan and sodium β-glycerophosphate by hydrogen bond action, form gel, finally give chitosan gel rubber pearl.
2. the preparation method of chitosan gel rubber pearl according to claim 1, it is characterised in that the method for comprising the following steps：
(1) preparation of shitosan/sodium β-glycerophosphate pentahydrate mixed solution：
1.2g-1.6g sodium β-glycerophosphate pentahydrates are dissolved in 2mL water, and the middle viscosity shitosan of 0.4g is dissolved in
In the acetum of 0.1mol/L；Under ice-water bath, to being slowly added dropwise sodium β-glycerophosphate five in the chitosan solution for having dissolved
Hydrate soln, obtains shitosan/sodium β-glycerophosphate pentahydrate mixed solution, and it is referred to as CS/ β-GP mixed solutions；
(2) regulation of shitosan/sodium β-glycerophosphate pentahydrate mixed solution pH value and the system of sodium dodecyl sulfate solution
It is standby：
Weigh 25g disodium hydrogen phosphate solids to be dissolved in 100ml water, dissolving obtains the disodium phosphate soln of saturation；To CS/ β-GP
The disodium phosphate soln of mixed solution and dripping saturation adjusts pH value between 6.9-7.1；Weigh 0.2g-0.8 dodecyls
Solid sodium sulfate is dissolved in 20mL water, prepares the lauryl sodium sulfate reception liquid of mass fraction 1%-4%, and it is referred to as SDS
Reception liquid；
(3) preparation of chitosan gel rubber pearl：
To be regulated during CS/ β-GP solution that pH value is 6.9-7.1 instills SDS reception liquids with liquid-transfering gun, shell is obtained after curing and is gathered
Sugared microcapsules, then with water washing is distilled 3 times, place into heating in water-bath, and the CS/ β-GP solution inside microcapsules is changed into
Gel, so as to obtain chitosan gel rubber pearl.
3. the preparation method of chitosan gel rubber pearl according to claim 2, it is characterised in that：Described middle viscosity shell gathers
Sugar, its viscosity is 200-400mPa.s, deacetylation >=90%.
4. the preparation method of chitosan gel rubber pearl according to claim 2, it is characterised in that：CS/ β-GP solution is instilled
In SDS reception liquids, its curing time is 50-70min.
5. the preparation method of chitosan gel rubber pearl according to claim 2, it is characterised in that：Adjusted using weakly alkaline solution
The pH value of CS/ β-GP solution, the weakly alkaline solution uses disodium hydrogen phosphate or potassium dihydrogen phosphate.
6. the preparation method of chitosan gel rubber pearl according to claim 2, it is characterised in that：Chitosan microcapsules are changed into
During gel beads, bath temperature is 39-45 DEG C, and water bath time is 4-7min.
7. the preparation method of chitosan gel rubber pearl according to claim 2, it is characterised in that：Shitosan and β-phosphoglycerol
The mass ratio of sodium is 1/3-1/4.
8. in claim 1 to 7 any claim methods described prepare chitosan gel rubber pearl application, it is characterized in that the shell
Application of the polysaccharide gel pearl in small molecule dyes are contained.
9. application according to claim 8, it is characterised in that：The chitosan gel rubber pearl is to molecular weight between 350-800
Small molecule dyes have excellent a containing property, place 12 hours without substantially leakage, contain stability with good.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107855080A (en) * | 2017-10-30 | 2018-03-30 | 中国科学院过程工程研究所 | Polymer gel particle, its preparation method, include its composite gel particle and purposes |
| CN109627499A (en) * | 2018-11-30 | 2019-04-16 | 湖南工业大学 | A kind of preparation method of the biomass combined gel with shear thickening effect |
| CN109912251A (en) * | 2019-02-27 | 2019-06-21 | 南昌大学 | Fluorescent marker microcapsules and preparation method for cement matrix crack detection reparation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721655A (en) * | 2014-01-06 | 2014-04-16 | 武汉理工大学 | Preparation method of chitosan microcapsule with uniform size and controllable size |
| CN105147597A (en) * | 2015-10-28 | 2015-12-16 | 青岛高新区尚达医药研究所 | Thermo-sensitive marine organism gel |
| CN106040120A (en) * | 2016-05-24 | 2016-10-26 | 武汉理工大学 | Preparation method for SiO2 nanoparticle reinforced chitosan composite microcapsule |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721655A (en) * | 2014-01-06 | 2014-04-16 | 武汉理工大学 | Preparation method of chitosan microcapsule with uniform size and controllable size |
| CN105147597A (en) * | 2015-10-28 | 2015-12-16 | 青岛高新区尚达医药研究所 | Thermo-sensitive marine organism gel |
| CN106040120A (en) * | 2016-05-24 | 2016-10-26 | 武汉理工大学 | Preparation method for SiO2 nanoparticle reinforced chitosan composite microcapsule |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107855080A (en) * | 2017-10-30 | 2018-03-30 | 中国科学院过程工程研究所 | Polymer gel particle, its preparation method, include its composite gel particle and purposes |
| CN107855080B (en) * | 2017-10-30 | 2020-09-08 | 中国科学院过程工程研究所 | Polymer gel particle, preparation method thereof, composite gel particle containing polymer gel particle and application |
| CN109627499A (en) * | 2018-11-30 | 2019-04-16 | 湖南工业大学 | A kind of preparation method of the biomass combined gel with shear thickening effect |
| CN109627499B (en) * | 2018-11-30 | 2020-11-27 | 湖南工业大学 | Preparation method of biomass composite gel with shear thickening effect |
| CN109912251A (en) * | 2019-02-27 | 2019-06-21 | 南昌大学 | Fluorescent marker microcapsules and preparation method for cement matrix crack detection reparation |
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