CN101157760A - Preparation of gels derived from carboxymethyl cellulose alkali metal salt - Google Patents
Preparation of gels derived from carboxymethyl cellulose alkali metal salt Download PDFInfo
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Abstract
A method of preparing a gel from carboxymethyl cellulose alkali metal salt, which is an anionic cellulose derivative, by using acid or acid solution. To increase the strength and the elasticity of a gel, a water-insoluble metal compound or organic reinforcement is added when mixing. The obtained gel is one of environmentally friendly type gels because the raw material is derived from plant.
Description
Technical field
The present invention relates to a kind of by using acid or acid solution to cause that molecular linkage (crosslinked) the cause carboxymethyl cellulose alkali metal salt among the CMC (hereinafter referred is CMC) prepares the method for gel.
Background technology
CMC is one of water-soluble polymers of the most normal use at present.CMC is a powder white or that turn white, and becomes transparent, tasteless viscous solution by being dissolved in water.Because carboxymethyl cellulose is derived from natural pulp, CMC has high security.By the molecule of the CMC that is cross-linked with each other, the CMC molecule forms three-dimensional network structure.As a result, can obtain in network structure, stably to accommodate the CMC gel of water.Thereby the gel that is obtained can be widely used in food, medicine, daily necessities, refrigerant or material of construction etc.
The certain methods that is prepared gel by anionic water-soluble polymer is known; With multivalent metallic ion crosslinking polymkeric substance (referring to JP0790121A, JP11106561A, JP2000191802A and JP2005263858A) with linking agent cross-linked polymer (referring to JP2003190991A, JP09277421A and JP10251447A).By radiation through polymkeric substance and water mix prepared polymer paste (pastes) also can with crosslinked be incorporated in the polymkeric substance (referring to JP200582800A, JP20012703A; Bin Fei, RadoslawA, Wach, Hiroshi Mitomo, Fumio Yoshii and Tamikazu Kume, Journal of AppliedPolymer Science, 78,278-283 (2000); Fumio Yoshii, Long Zhao, Radoslaw A, Wach, Naotsugu Nagasawa, Hiroshi Mitomo and Tamikazu Kume, Nuclear Instruments andMethods in Physics Research B, 208 (2003) 320-324; Radoslaw A.Wach, HiroshiMitomo, Naotsugu Nagasawa and Fumio Yoshii, Radiation Physics and Chemistry, 68 (2003) 771-779).
Summary of the invention
Yet, a kind of possibility is arranged, that is: when polyvalent metal ion was used to prepare gel, polyvalent metal ion can be stayed in the gel.Use therein in the method for formation gel of linking agent, the use of formed gel is limited, because most of linking agent is all toxic.In radiation-induced gelation, must need large-scale device.
One of purpose of the present invention provides a kind of method of not using the preparation of polyvalent metal ion or linking agent derived from the gel of CMC.Described gel environmental sound and to human body safety, and this gel can be used for food and medicine.
Another object of the present invention provides a kind of method for preparing gel that can easily obtain snappiness, high-intensity environment-friendly type gel, and the gel that forms thus.
Principle of the present invention based on the inventor pass through use acid or acid solution to cause the new discovery that the molecular linkage cause CMC among the CMC prepares gel.
In making according to the gel of first embodiment of the invention, the anionic water-soluble polymer CMC with high security is used as original material.By being mixed with acid or acid solution, CMC forms gel.
In addition, in the preparing gel of second embodiment of the invention, gel forms slurry by CMC is mixed with water, follows, with in immersion acid of CMC slurry or the acid solution and form.
The mechanism reasoning that forms gel by mixed C MC and acid is as follows.Infrared absorption (IR) spectrum by mixed C MC and sour formed gel is measured.No matter the kind of acid, described infrared absorption spectrum almost is identical, shows, no matter the kind of acid, gel has structure much at one.Can think that according to the thermogravimetric analysis of gel and the measuring result of differential thermal analysis described gel is not by the formed gel of the covalent linkage of new introducing, but by the formed gel of the polymerization of CMC molecular chain.When employed CMC is sodium salt, the sodium in the carboxyl of CMC is replaced by hydrogen to be become-form of COOH.Therefore, the extension of CMC molecular chain is suppressed, and the polymerization of CMC molecule takes place to form hydrogen bond.As a result, gel formation.Can think, when a part of carboxyl with-when the COONa form exists, can form wherein hydrogen bond softer gel seldom.
In order to increase the crosslinked of CMC, after with CMC and acid or acid solution mixing, can implement ionizing rays to mixing solutions.Also can then described mixture be immersed the CMC gel enforcement ionizing rays of manufacturing in acid or the acid solution to by first mixed C MC and water, crosslinked in gel, to cause.Also can carry out radiation, it be immersed in acid or the acid solution to form hardening gel then CMC slurry by mixed C MC and water manufacturing.By radiation CMC, can be incorporated among the CMC crosslinked, thereby increase the gel umber.
Because gel can according to above-mentioned embodiment, not need to use virose reagent so far only by mixed C MC and acid or acid solution formation.In addition, because ionizing rays is not a prerequisite, so in preparing gel, needn't use special device such as radiation device.Especially because by the formed gel of aforesaid method have in the conventional gel the good modulus of compression that can not obtain, and high thermotolerance and acid resistance, expection can have widely uses.
Forming according to third embodiment of the invention in the method for gel, can be only by mixing the formation gel as CMC, acid or acid solution and the water-insoluble metallic compound of main component.The order by merging of CMC, acid or acid solution and water-insoluble metallic compound is not restricted to above-mentioned order, and therefore, this method is extremely simple.
Preferably, in the 3rd embodiment, the weight of CMC is less than 65% of the original material gross weight.When the weight of CMC surpassed 65%, it was difficult mixing them, thereby it is unfavorable surpassing 65%.
For the usage quantity of acid or acid solution, in the 3rd embodiment, the 35%-95% of original material gross weight is an ideal.When acid or acid solution during less than 35wt%, gel can not be formed uniformly, when it surpasses 95wt%, and the preparation of the gel difficulty that becomes.In addition, for the usage quantity of water-insoluble metallic compound, the 1%-30% of original material gross weight is an ideal.When metallic compound during less than 1wt%, intensity can be improved hardly, and when it surpassed 30wt%, gel can not be formed uniformly.Preferably, hydrochloric acid or hydrochloric acid soln are as acid or acid solution, and aluminum oxide is used as according to water-insoluble metallic compound in the formation method of the 3rd embodiment.By mixing three kinds of components of aforesaid CMC, hydrochloric acid or hydrochloric acid soln and aluminum oxide, can easily obtain high strength and elastomeric gel.
Forming according to four embodiment of the invention in the method for CMC gel, acid or acid solution and organic enhancing body are being joined among the CMC, then these components are being mixed to obtain the CMC gel.
In the 4th embodiment, the content range of CMC is for by adding the 3%-64% of acid or acid solution and the organic enhancing body mixture total weight amount of manufacturing in the CMC.
In the 4th embodiment, using hydrochloric acid or hydrochloric acid soln is ideal as acid or acid solution.
In the 4th embodiment, using and being selected from one or more organic compound that comprise in Microcrystalline Cellulose, pectin, alginic acid, gelling gum, cm-chitosan, polyethylene and polyacrylic group is ideal as organic enhancing body.
Though the water-insoluble metallic compound is added into elasticity and the intensity to improve gel in the above-described 3rd embodiment, when being handled, it may cause reducing as the value of environment-friendly type gel according to the formed gel of this method.Yet,, when refuse is handled, may not can reduce as the value of environment-friendly type gel because in the 4th embodiment, used organic enhancing body.
Description of drawings
Figure 1A is the schema according to the gel process for preparing of first embodiment of the invention, in this method, by mixed C MC and acid or acid solution formation gel;
Figure 1B is the schema according to the gel process for preparing of second embodiment, in this method, will immerse in acid or the acid solution by the slurry that joins water among the CMC to be obtained and form gel;
Fig. 2 has shown by mixing the performance synoptic diagram of the gel that various CMC and phosphoric acid obtains;
Fig. 3 A is the chart that concerns between the explanation viscosity of CMC and the gel umber shown in Fig. 2;
Fig. 3 B is the chart that concerns between the gel water absorbability shown in illustration substitution value (degree of etherification) and Fig. 2;
Fig. 4 is the synoptic diagram that shows the hardness of the every kind of CMC gel that is obtained by mixed C MC1380 and various acid solution;
Fig. 5 is the chart that concerns between demonstration and CMC blended phosphoric acid concentration and the gel umber;
Fig. 6 A is the schema that shows method prepare modified gel C, in this method, to by mixed C MC and acid or gel enforcement radiation that acid solution obtained;
Fig. 6 B and Fig. 6 C are respectively the gel phase ratios that shows with radiation crosslinking, by the synoptic diagram of radiation gamma-rays in by mixed C MC and acid or gel that acid solution obtained to concern between the gel umber of preparation gel and the absorption dose;
Fig. 7 is the schema that shows method prepare modified gel D, in this method, will immerse in acid or the acid solution by the slurry that joins water among the CMC to be obtained, then to the gel radiation gamma-rays that is obtained with formation modified gel D;
Fig. 8 is an illustration according to the chart that concerns between the absorption dose of the formed modified gel of schema shown in Fig. 7 and the gel umber;
Fig. 9 is the schema that shows preparation modified gel method, in this method, to by water is added the slurry radiation gamma-rays that is obtained among the CMC, then the gel that is obtained is immersed in acid or the acid solution to form modified gel E earlier;
Figure 10 is an illustration according to the chart that concerns between the absorption dose of the prepared modified gel of the schema shown in Fig. 9 and the gel umber;
Figure 11 is the schema according to the gel process for preparing of third embodiment of the invention, by this method, can form snappiness and high-intensity gel F;
Figure 12 is the schema according to the gel process for preparing of four embodiment of the invention, by this method, can form snappiness and high-intensity gel G;
Figure 13 is the synoptic diagram that shows according to the formed gellifying property of gel process for preparing shown in Figure 12.
Embodiment
Hereinafter with reference to the accompanying drawings, be elaborated based on the method for embodiment to formation CMC gel of the present invention.
＜the first embodiment 〉
Test examples 1 (gel A)
Figure 1A has shown the preparing gel outline flowchart.Have different degree of substitution (degree of etherification) and viscosity (viscosity of 25 ℃ of 1% solution of measuring down when various, if viscosity height, molecular weight is also high) CMC (Daicel compound Industrial Co., Ltd. make, referring to Fig. 2) when mixing with the phosphoric acid solution of 3mol/l, gelation all takes place in all CMC.The gel of Zhi Zaoing (gel A hereinafter referred to as) has higher modulus of compression like this.Uncrosslinked CMC and phosphoric acid can clean gel A by water and remove, and the ratio of water insoluble active ingredient can be defined as the gel umber.This results are shown among Fig. 2 and Fig. 3 A.
Fig. 3 A illustration the relation between the gel umber shown in CMC viscosity and Fig. 2, Fig. 3 B illustration the relation between the water absorbability of the gel shown in the substitution value of CMC (degree of etherification) and Fig. 2.Can learn that from Fig. 3 A the gel umber increases along with the increase of CMC viscosity.Similarly, can learn the trend that water absorbability increases with the substitution value (degree of etherification) of CMC from Fig. 3 B.By confirming that to the measurement of the phosphorus in the gel phosphoric acid is not stayed in the gel by EDX (energy dispersive Xray fluorescence spectrometer) and ICP (inductively coupled plasma mass spectrograph).
Though above-mentioned test examples relates to by mixed C MC and phosphoric acid and prepares gel A, the similar test that other acid is implemented is finished.The results are shown among Fig. 4 of they.From Fig. 4, can learn,, also can form CMC gel A with permanent hardness (N) even any one of common CMC1380 and formic acid, citric acid, acetate, lactic acid, phosphoric acid, toxilic acid, oxalic acid and hydrochloric acid soln mixed.Further, learn, can form soft gel with respect to xitix.The pH value of acid is low more, and it is high more that the gel umber becomes, and the hardness of gel increases.Therefore can learn, kind that herein needn't specified acid, the hardness of gel can be adjusted by the kind and the concentration that change acid.
Can learn that from the test-results shown in Fig. 2 CMCs all on the market can both use.That is, can learn that all CMCs can be by mixing and gelation with acid or acid solution.Though substitution value (degree of etherification) and viscosity are arbitrarily, the gel A with different performance can be prepared by the CMC that use has different degree of substitution (degree of etherification) and a molecular weight.Under CMC concentration condition with higher, the speed of gelation is fast, and when concentration was hanged down, speed was slow.The concentration range of preferred CMC is 2.5wt%-40wt%, and in this scope, CMC can mix equably with acid or acid solution.
Combination according to CMC and acid can form the gel with different performance.Though depend on the kind of acid, the concentration of acid is different, and the acid of 0.1mol/l or greater concn generally is preferred.When using high density sour, gelation speed is fast, gel umber height, and form hard gel.This true example as an illustration, the relation between phosphoric acid concentration (%) and the gel umber (%) is shown among Fig. 5.Rise to about 7.8% phosphoric acid, the gel umber is increased to about 72.4% fast.Then, if its concentration increases, the gel umber also little by little increases.Further, the gel umber increases according to the increase of CMC concentration.According to contriver's experiment, when with the mixing of 3mol/l phosphoric acid in the concentration of CMC when being 5,10 and 20%, the gel umber is respectively 21.5,85.8 and 86.1.
Temperature when CMC mixes with acid or acid solution is arbitrarily.Usually, when the temperature when mixing was high more, gelation was carried out rapidly more.Yet, need avoid taking place for example 70 ℃ of mixing down of temperature of hydrolysis at CMC.In addition, CMC being mixed the back time that is kept with acid or acid solution is arbitrarily.When the concentration of CMC and acid when high, gelation is carried out immediately, that is to say, it takes place simultaneously at blended.On the other hand, when their concentration was hanged down, gelation was carried out comparatively slow.Although the gel umber increases according to mixed retention time usually, be reflected in about 24h and finish.
Test examples 2 (gel C)
The preparation procedure of modified gel C briefly is shown among Fig. 6 A.Can make the CMC slurry of CMC by mixing 20wt% and water manufacturing and CMC by mixing 20wt% and the formed CMC gel of the phosphoric acid A of 1mol/l.The latter forms according to the schema shown in Figure 1A.Respectively to these CMC slurries and CMC gel A radiation gamma-rays.As a result, obtain new modified gel (modified gel C hereinafter referred to as).Measure the gel umber (%) and the water absorbability (gram water/gram gel) of each CMC slurry and CMC gel C.The dosage that the CMC slurry is absorbed is 5kGy, 10kGy, 20kGy, 30kGy, 40kGy and 50kGy.The dosage that CMC gel A is absorbed is 5kGy and 10kGy.Measured numerical value is shown among Fig. 6 B and Fig. 6 C.
Can easily learn, be not transformed into gel by radiation by the CMC of the certain percentage of acid cure gel.According to the radiation at 5KGy place, the gel umber increases, and water absorbability reduces.That is to say that A can obtain the higher gel of intensity by radiation CMC gel.And, mixing in the gel that is obtained with acid or acid solution by CMC, and obtain the CMC slurry by mixed C MC and water and implement the radiating situation and compare to aforesaid, gelation low dosage ground carries out.In addition, by using in the formed gel of high concentrated acid, the water absorbed dose seldom, and the influence of raying hardly.
＜the second embodiment 〉
Test examples 3 (gel B)
The preparation process of gel B briefly is shown among Figure 1B.When the prepared CMC slurry of water of CMC that will be by mixing 20wt% and 80wt% immerses in the hydrochloric acid of 0.1mol/l, can form gel (gel B hereinafter referred to as).The gel umber of preparation is 35%, and the water absorbed dose of every 1g desiccant gel is 340g.When the CMC slurry being immersed in acid or the acid solution, gelation takes place in acid solution, the concentration of described acid solution will be lower than the concentration of the acid when CMC mixed with acid or acid solution.
Test examples 4 (gel D)
The preparation flow of modified gel D briefly is shown among Fig. 7.To by the CMC slurry being immersed CMC gel (gel B) the radiation gamma-rays that is obtained in acid or the acid solution, the result forms modified gel (hereinafter becoming gel D).The numeric data of modified gel D after the gamma-rays radiation is shown among Fig. 8.Among Fig. 8, solid line and dotted line are represented the performance by the modified gel D that 6h and 24h in the CMC slurry immersion acid solution is prepared respectively.According to the chart among Fig. 8, when the concentration of acid was enough hanged down, by the radiation gamma-rays, the gel umber significantly increased.Yet it has shown the feature that flattens after the dosage that gamma-rays absorbed surpasses 10KGy substantially.On the other hand, when acid concentration is enough high, can obtain high gel umber by immersing 6h, even and the radiation gamma-rays, the gel umber can not improve yet.
Test examples 5 (gel E)
The radiation crosslinking CMC gel that will be at the 5KGy place prepares to the formed CMC slurry of the water radiation gamma-rays of CMC by mixing 20wt% and 80wt% immerses in the hydrochloric acid soln of 0.1mol/l, the weight of described hydrochloric acid soln is 10 times of radiation crosslinking CMC gel, and described slurry at room temperature keeps 16h.As a result, the gel umber is increased to 73% from 33%, but the water absorbed dose of the desiccant gel of every 1g is reduced to 90g from 887g.This shows by gel is immersed and carries out physical crosslinking in the hydrochloric acid soln, has formed a kind of new modified gel (gel E hereinafter referred to as).Like this gel of Huo Deing demonstrate with at the gel umber of 20KGy place radiation crosslinking gel gel umber and the water absorbability suitable with water absorbability.Therefore, can learn that the processing in the acid helps the reduction of absorption dose.In addition, by the radiation crosslinking gel being immersed the gel that can obtain higher-strength in acid or the acid solution.
The process for preparing above-mentioned gel E is shown among Fig. 9.And, be shown among Figure 10 according to the gel umber of the prepared gel E of the schema of Fig. 9.Among Figure 10, HCl represents hydrochloric acid, and PA represents phosphoric acid, and CA represents that citric acid and M represent mol/l.Learn easily that from the chart of Figure 10 the gel umber of gel E changes hardly, irrelevant with absorption dose.
Though in above-mentioned modified gel preparation method's a example, to by mixed C MC and acid or gel radiation gamma-rays that acid solution obtained, radiation is not restricted to gamma-rays, but comprises the electron beam that is used for the radiation crosslinking technical field.In addition,, can be clear that from the principle of the embodiment of the invention though only used a kind of acid in the above-mentioned example, though in conjunction with and use two or more acid, it also is possible forming similar gel.Further, though used the term that is called gel A, gel B, gel C, gel D, gel E in the above description; But these terms are not the molecular bonding structure that is used to illustrate formed gel, but help to understand gel process for preparing.
＜the three embodiment 〉
Hereinafter 11 pairs of methods that prepare gel according to third embodiment of the invention are illustrated with reference to the accompanying drawings.Figure 11 is the schema according to the gel process for preparing of third embodiment of the invention, by this method, has formed snappiness and high-intensity gel.
Among Figure 11, CMC, acid or acid solution and water-insoluble metallic compound are mixed with mixing machine.As a result, form the CMC gel.
The degree of etherification of employed CMC and viscosity are arbitrarily.Viscosity table herein is shown in the viscosity of 25 ℃ of 1wt%CMC that measure down.Higher viscosity means higher molecular weight indirectly.The CMC of powder or aqueous solution form can mix with acid or acid solution well.In order more easily to mix the solution of preferred 5wt% or greater concn.Concerning acid, any organic acid or mineral acid are acceptable.Further, Suan kind is arbitrarily.For example, can use hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphonic acid, nitric acid, formic acid, acetate, lactic acid, succsinic acid, methylene-succinic acid, toxilic acid, oxalic acid and citric acid etc.Though these sour concentration are arbitrarily, in order easily to mix, be preferably 0.1mol/l or more than.
The employed water-insoluble metallic compound of third embodiment of the invention includes, but are not limited to a certain water-insoluble metallic compound.Operable metallic compound comprises metal oxide such as titanium oxide, ferric oxide, aluminum oxide, manganese oxide and Manganse Dioxide and metal-salt such as barium sulfate, barium carbonate, barium phosphate, lime carbonate and calcium phosphate.Especially, preferred aluminum oxide.
Temperature when CMC mixes with acid or acid solution is arbitrarily.Usually, the increase of temperature during according to mixing, gelation is carried out rapidly.Yet, need avoid taking place for example 70 ℃ of mixing down of temperature of hydrolysis at CMC.In addition, CMC and water-insoluble metallic compound and acid or acid solution being mixed the time that the back kept can at random be provided with.When the concentration of the CMC aqueous solution and acid solution was high, gelation was carried out immediately.Gel umber, the gelation speed of water-insoluble gel increase according to mixed retention time usually.
[test examples 1 of the 3rd embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and the commercial anatase-type titanium oxide of 5g (202-01725 of Wake pure compound Industrial Co., Ltd manufacturing) join in the 1mol/l hydrochloric acid of 75g, mixed 20 minutes under 2000rpm by " Awatori Rentaro " super mixer that uses THINKY company to make, froth breaking is 10 minutes then.Mixed sample slurry is put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes, and molded.Preservation is after 7 days down at 30 ℃ through molded sample, and the small table trier EZTest that makes with Shimadzu company measures physicals.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity of gel is measured.Breaking tenacity is 0.88N/mm
2In addition, with this trier 50% o'clock the modulus of compression that gel is compressed to its initial thickness is measured.Modulus of compression is 1.12N/mm
2Even after twice 50% compressions, gel is also keeping previous shape, and gel demonstrates high restorer and snappiness.
[test examples 2 of the 3rd embodiment]
(degree of etherification is 1.36 with the commercial CMC of 40g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and the commercial aluminum oxide of 13.6g (manufacturing of Wake pure compound Industrial Co., Ltd 01201965) join in the 1mol/l hydrochloric acid of 46.4g, mixed 20 minutes under 2000rpm by " Awatori Rentaro " super mixer that uses THINKY company to make, froth breaking is 10 minutes then.It is thick to be expanded to 10mm through blended CMC slurry, and holes with cork borer.Sample through boring, is measured the breaking tenacity of gel by the Strograph VE5D that uses Toyo Seiki to make after 7 days in preservation under 30 ℃.Breaking tenacity is 5.87N/mm
2In addition, the small table trier EZTest that makes with Shimadzu company measures 50% o'clock the modulus of compression that gel is compressed to its initial thickness.Modulus of compression is 7.99N/mm
2Even after twice 50% compressions, gel is also keeping previous shape, and gel demonstrates high restorer and snappiness.
[comparative example 1 of the 3rd embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) join in the 1mol/l hydrochloric acid of 80g, and passing through to use " Awatori Rentaro " super mixer of THINKY company manufacturing under 2000rpm, to mix 20 minutes, froth breaking is 10 minutes then.Put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes through the blended sample slurry, and molded.After preserving 7 days under the 30C, the small table trier EZTest that makes with Shimadzu company measures physicals through molded sample.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity of gel is measured.Breaking tenacity is 0.44N/mm
2In addition, with this trier 50% o'clock the modulus of compression that gel is compressed to its initial thickness is measured.Modulus of compression is 0.16N/mm
2After one time 50% compression, this gel no longer keeps previous shape.
[comparative example 2 of the 3rd embodiment]
(degree of etherification is 1.36 with the commercial CMC of 40g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) join in the 1mol/l hydrochloric acid of 60g, mixed 20 minutes under 2000rpm by " Awatori Rentaro " super mixer that uses THINKY company to make, froth breaking is 10 minutes then.It is thick and hole with cork borer to be expanded to 10mm through the blended sample slurry.Preservation is after 7 days down at 30 ℃ for sample through holing, and the small table trier EZTest that makes with Shimadzu company is measured the breaking tenacity of gel.By coming the breaking tenacity of gel is measured with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm.Breaking tenacity is 1.03N/mm
2
The gel that forms according to third embodiment of the invention and by using polyvalent metal ion or the formed gel phase ratio of linking agent, has snappiness.And because do not need expensive radiation devices, it is possible cheaply and easily preparing gel.In addition, with wherein only the gel formation method of use acid is different, can form high-intensity gel.Because starting material are plant-derived, the gel that is obtained is a kind of environment-friendly type gel.
Above-mentioned CMC gel can be used for extensive fields, and for example agricultural, industry and medical are preferred for change livestock waste treatment agent, waste water conditioner, deodoring materials, support of the catalyst, vibration absorptive material, are used for the medical applications of jointing material and Patty material etc.
＜the four embodiment 〉
At last, with reference to Figure 12 and Figure 13 the 4th embodiment of the present invention is illustrated.Figure 12 is the gel process for preparing schema according to four embodiment of the invention, by this method, can form and has snappiness and high-intensity gel.In the method, at first acid or acid solution and organic enhancing body are joined among the CMC.With stirrer etc. their are mixed and to form gel.That is to say, form the gel (hereinafter being also referred to as " CMC gel G ") of CMC.
The CMC an alkali metal salt that is used for four embodiment of the invention comprises for example sodium salt, sylvite and ammonium salt.The degree of etherification of used CMC and viscosity are arbitrarily.Viscosity table herein is shown in 25 ℃ of 1wt%CMC viscosity in aqueous solution of measuring down.Higher viscosity means higher molecular weight indirectly.The CMC of powder or aqueous solution form can mix with acid or acid solution well.In order more easily to mix the solution of preferred 5wt% or greater concn.
For the concentration of CMC, can use the CMC of the 3-64% of the mixture total weight amount that comprises CMC, acid or acid solution and organic enhancing body, preferred 10-34%.When the weight of CMC less than 3% the time, can not obtain to have the CMC gel of sufficient intensity.In addition, when the weight of CMC surpasses 64%, may be difficult to mix equably.
Any one acid of organic acid and mineral acid all can be used as the acid that is used for the 4th embodiment.Further, Suan kind is arbitrarily.For example, can use hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphonic acid, nitric acid, formic acid, acetate, lactic acid, succsinic acid, methylene-succinic acid, toxilic acid, oxalic acid and citric acid etc., perhaps their acid solution.These acid or acid solution can use separately or be used in combination.For obtaining high strength and elastomeric CMC gel, preferably use hydrochloric acid or hydrochloric acid soln.
Though the concentration of acid solution is arbitrarily, in order easily to mix the scope of preferred 0.1mol/l-3mol/l.Usually, when the concentration of CMC and acid when high, gelation speed increases.Therefore, when the concentration of acid solution was too high, gelation was carried out at once, and it may be difficult that organic enhancing body is mixed with CMC.
For the amount of acid or acid solution, can use the 35-95% of the mixture total weight amount that comprises CMC, acid or acid solution and organic enhancing body, preferred 60-90%.When the weight of acid or acid solution less than 35% the time, the CMC gel becomes inhomogeneous, and can not obtain the CMC gel of sufficient intensity.In addition, when the weight of acid or acid solution surpassed 95%, it was difficult forming gel.
The organic enhancing body that is used for the 4th embodiment is extremely important to the elasticity and the intensity that improve the CMC gel that is obtained.High strength and elastomeric CMC gel can obtain by add organic enhancing body in CMC and acid or acid solution.Described organic enhancing body comprises for example derivatived cellulose, saccharan, amino acid, polymkeric substance and carbohydrate etc.Specifically, it comprises: derivatived cellulose such as Microcrystalline Cellulose, cellulose triacetate, Vltra tears, ethyl cellulose and methylcellulose gum; Saccharan such as agar, alginic acid, gelling gum, pectin, the purple psyllium seed gum of flax, guar gum, gum arabic, cm-chitosan, arabogalactan, carrageenin, tamarind seed gum, mannosans, chitin and chitosan; Polymkeric substance such as gelatin, polyvinyl alcohol, polyacrylic acid, Polyvinylpyrolidone (PVP), polyethylene and poly(lactic acid) etc.; With amino acid such as glycine, L-Ala and L-glutamic acid; And carbohydrate such as sucrose, glucose and fructose.These materials can use separately or be used in combination.In order to obtain high strength and elastomeric CMC gel, preferred one or more organic compound that are selected from the group that comprises Microcrystalline Cellulose, pectin, alginic acid, gelling gum, cm-chitosan, polyethylene and poly(lactic acid) that use.
For the usage quantity of organic enhancing body, can use the 1-30% of the mixture total weight amount that comprises CMC, acid or acid solution and organic enhancing body, preferred 2-10%.When the weight of organic enhancing body less than 1% the time, may not can obtain sufficient intensity and elastic CMC gel.In addition, when the weight of organic enhancing body surpassed 30%, it is inhomogeneous that the CMC gel may become, and may not can obtain the CMC gel of sufficient intensity.
As mentioned above, the CMC gel can be by adding earlier acid or acid solution and organic enhancing body in CMC, and with stirrer etc. their are mixed to form gel and to obtain.The order of mixed C MC, acid or acid solution and organic enhancing body is arbitrarily.For example, with among organic enhancing body adding CMC and after mixing, acid or acid solution are added wherein also mixing.In addition, it also is possible simultaneously organic enhancing body and acid or acid solution being added among the CMC and their are mixed.The commercial stirrer of three kinds of compositions of any MC of mixed C effectively, acid or acid solution and organic enhancing body all can be as above-mentioned stirrer.Further, be possible directly with the spiral type stirrer mixing material.In addition, " Awatori Rentaro " super mixer that uses THINKY company to make also is possible.Because revolution during the rotation of the raw-material container of the storage of these mixing tanks, can reach uniform stirring and in raw material, do not stay a large amount of bubbles.
Need avoid taking place for example 70 ℃ of mixing down of temperature of hydrolysis at CMC.Usually, when the temperature when mixing was high more, gelation was carried out rapidly more.Therefore, consider gelation process and degree of mixing determined according to the kind of used organic enhancing body and CMC, gelation is carried out by mixing temperature correctly is set with its usage quantity.Target CMC gel can obtain by keep certain hour after mixing.Though the time that is kept after CMC mixes with acid or acid solution is arbitrarily, the gel umber increases according to mixed retention time usually.
[test examples 1 of the 4th embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and the commercial Microcrystalline Cellulose of 5g (the column type chromatogram that is used for the manufacturing of Funakoshi company) join the 1mol/l hydrochloric acid of 75g, mixed 20 minutes under 2000rpm by " Awatori Rentaro " super mixer that uses THINKY company to make, froth breaking is 10 minutes then.Sample slurry is put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes, and moulding.Sample through moulding descends preservation after 7 days at 30 ℃, and the small table trier EZTest that makes with Shimadzu company measures physicals.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity and the modulus of compression of gel are measured.Breaking tenacity is 1.39N/mm
2, modulus of compression is 0.136N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Maximum stress is 0.26N/mm
2Even after twice 50% compressions, gel is still keeping previous shape, gel demonstrates high restorer and snappiness.
[test examples 2 of the 4th embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and the commercial pectin of 10g (the 1NAGEL JP-20 of Ina foodstuffs industry company limited manufacturing) join in the 0.75mol/l hydrochloric acid of 70g, mixed 20 minutes under 2000rpm by " Awatori Rentaro " super mixer that uses THINKY company to make, froth breaking is 10 minutes then.It is thick that sample slurry is expanded to 10mm, and hole with cork borer.Preservation is after 5 days down at 30 ℃ for sample through holing, and the small table trier EZTest that makes with Shimadzu company measures the breaking tenacity and the modulus of compression of gel.Breaking tenacity is 1.59N/mm
2, modulus of compression is 0.169N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Maximum stress is 0.24N/mm
2Even after twice 50% compressions, gel is still keeping previous shape, and gel demonstrates high restorer and snappiness.
By adopting the strip specimen of thick 0.5mm, wide 8mm, tension test is implemented with the small table trier EZTest that Shimadzu company makes.Breaking tenacity is 4.15N/mm
2, Young's modulus is 2.48N.
[test examples 3 of the 4th embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and the commercial alginic acid of 5g (the INAGEL GS-30 of Ina foodstuffs industry company limited manufacturing) join in the 1mol/l hydrochloric acid of 75g, mixed 20 minutes under 2000rpm by the Awatori Rentaro super mixer that uses THINKY company to make, froth breaking is 10 minutes then.Sample slurry is put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes, and moulding.Sample through moulding descends preservation after 7 days at 30 ℃, and the small table trier EZTest that makes with Shimadzu company measures the physicals of gel.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity and the modulus of compression of gel are measured.Breaking tenacity is 1.05N/mm
2, modulus of compression is 0.177N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Maximum stress is 0.28N/mm
2Even after twice of 50% implementation of compression, gel is still keeping previous shape, and gel demonstrates high restorer and snappiness.
[test examples 4 of the 4th embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and the commercial gelling gum of 5g (the INAGEL GS-15 of Ina foodstuffs industry company limited manufacturing) join in the 1mol/l hydrochloric acid of 75g, mixed 20 minutes under 2000rpm by the Awatori Rentaro super mixer that uses THINKY company to make, froth breaking is 10 minutes then.Sample slurry is put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes, and moulding.Sample through moulding descends preservation after 7 days at 30 ℃, and the small table trier EZTest that makes with Shimadzu company measures the physicals of gel.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity and the modulus of compression of gel are measured.Breaking tenacity is 1.05N/mm
2, modulus of compression is 0.160N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Maximum stress is 0.23N/mm
2Even after twice 50% compressions, gel is still keeping previous shape, and gel demonstrates high restorer and snappiness.
[test examples 5 of the 4th embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and 5g commercialization cm-chitosan join in the 1mol/l hydrochloric acid of 75g, mixed 20 minutes under 2000rpm by the Awatori Rentaro super mixer that uses THINKY company to make, froth breaking is 10 minutes then.Sample slurry is put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes, and moulding.Sample through moulding descends preservation after 7 days at 30 ℃, and the small table trier EZTest that makes with Shimadzu company measures the physicals of gel.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity and the modulus of compression of gel are measured.Breaking tenacity is 2.58N/mm
2, modulus of compression is 0.150N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Maximum stress is 0.10N/mm
2Even after twice of 50% implementation of compression, gel is still keeping previous shape, and gel demonstrates high restorer and snappiness.
[test of the 4th embodiment implements 6]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and 5g commercialization polyethylene join in the 1mol/l hydrochloric acid of 75g, mixed 20 minutes under 2000rpm by the Awatori Rentaro super mixer that uses THINKY company to make, froth breaking is 10 minutes then.Sample slurry is put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes, and moulding.Sample through moulding descends preservation after 7 days at 30 ℃, and the small table trier EZTest that makes with Shimadzu company measures the physicals of gel.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity and the modulus of compression of gel are measured.Breaking tenacity is 1.06N/mm
2, modulus of compression is 0.154N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Even after twice 50% compressions, gel is still keeping previous shape, and gel demonstrates high restorer and snappiness.
[test examples 7 of the 4th embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) and 5g commercialization poly(lactic acid) join in the 1mol/l hydrochloric acid of 75g, mixed 20 minutes under 2000rpm by the Awatori Rentaro super mixer that uses THINKY company to make, froth breaking is 10 minutes then.Sample slurry is put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes, and moulding.Sample through moulding descends preservation after 7 days at 30 ℃, and the small table trier EZTest that makes with Shimadzu company measures the physicals of gel.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity and the modulus of compression of gel are measured.Breaking tenacity is 2.12N/mm
2, modulus of compression is 0.139N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Maximum stress is 0.17N/mm
2Even after twice 50% compressions, gel is still keeping previous shape, and gel demonstrates high restorer and snappiness.
[comparative example 1 of the 4th embodiment]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) join in the 1mol/l hydrochloric acid of 80g, mixed 20 minutes under 2000rpm by the Awatori Rentaro super mixer that uses THINKY company to make, froth breaking is 10 minutes then.Sample slurry is put into the framework that the Teflon (registered trademark) of diameter 20mm, thickness 10mm makes, and moulding.Sample through moulding descends preservation after 7 days at 30 ℃, and the small table trier EZTest that makes with Shimadzu company measures the physicals of gel.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity and the modulus of compression of gel are measured.Breaking tenacity is 1.01N/mm
2, modulus of compression is 0.105N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Maximum stress is 0.14N/mm
2After 50% compression, gel can not keep previous shape.
[the 4th embodiment relatively execute example 2]
(degree of etherification is 1.36 with the commercial CMC of 20g, 25 ℃ of following 1wt% viscosity in aqueous solution are 1640mPas, Daicel compound industry company limited makes) join in the 0.75mol/l hydrochloric acid of 80g, mixed 20 minutes under 2000rpm by the Awatori Rentaro super mixer that uses THINKY company to make, froth breaking is 10 minutes then.It is thick and hole with cork borer that sample slurry is expanded to 10mm.Preservation is after 5 days down at 30 ℃ for sample through holing, and the small table trier EZTest that makes with Shimadzu company measures physicals.By with the made compression clamp compression gel of the Teflon (registered trademark) of diameter 50mm, the breaking tenacity and the modulus of compression of gel are measured.Breaking tenacity is 1.22N/mm
2, modulus of compression is 0.116N/mm
2In addition, with this trier 50% o'clock the maximum stress that gel is compressed to its initial thickness is measured.Maximum stress is 0.13N/mm
2By adopting the strip specimen of thick 0.5mm, wide 8mm, tension test is implemented with the small table trier EZTest that Shimadzu company makes.Breaking tenacity is 3.63N/mm
2, Young's modulus is 1.16N.
Above-mentioned the results are shown among Figure 13.Fig. 13 is the performance synoptic diagram that show according to gel that gel process for preparing obtains shown in Figure 12, among Figure 13, less than 1.05 (N/mm
2) breaking tenacity be evaluated as " * " (1 minute), 1.05-1.30 (N/mm
2) be evaluated as " Δ " (2 minutes), greater than 1.30 (N/mm
2) be evaluated as " zero " (3 minutes).Less than 0.110 (N/mm
2) modulus of compression be evaluated as " * " (1 minute), 0.110-0.130 (N/mm
2) be evaluated as " Δ " (2 minutes), greater than 0.130 (N/mm
2) be evaluated as " zero " (3 minutes).Less than 0.15 (N/mm
2) the maximum stress in 50% when compression be evaluated as " * " (1 minute), 0.15-0.20 (N/mm
2) be evaluated as " Δ " (2 minutes), greater than 0.20 (N/mm
2) be evaluated as " zero " (3 minutes).
According to four embodiment of the invention, because do not need expensive radiation devices, it is possible cheaply and easily preparing gel.In addition, with wherein only the gel formation method of use acid is different, can form high-intensity gel.Because starting material are plant-derived, the gel that is obtained is a kind of environment-friendly type gel.
Described CMC gel can be used for extensive fields, for example agricultural, industry and medical treatment food is preferred for change livestock waste treatment agent, waste water conditioner, deodoring materials, support of the catalyst, energy-absorbing material, is used for the medical applications of jointing material and Patty material etc.
Claims (17)
1. one kind prepares the method for gel by carboxymethyl cellulose alkali metal salt (CMC), causes molecular linkage among the CMC by using acid or acid solution.
2. the method for preparing gel according to claim 1 wherein, is implemented ionizing rays to the gel that described its starting material are CMC.
3. one kind prepares the method that its starting material are the physical gel of carboxymethyl cellulose alkali metal salt (CMC), by acid or acid solution are mixed with CMC.
4. the method for preparing physical gel according to claim 3 wherein, is implemented ionizing rays to obtain modified gel after mixing.
5. one kind prepares the method that its starting material are the physical gel of carboxymethyl cellulose alkali metal salt (CMC), forms slurry by CMC is mixed with water, then, described slurry is immersed in acid or the acid solution.
6. the method for preparing physical gel according to claim 5 wherein, is implemented ionizing rays to obtain gel after immersion.
7. one kind prepares the method that its starting material are the gel of carboxymethyl cellulose alkali metal salt (CMC), implement ionizing rays to form the radiation crosslinking gel by CMC is mixed the back with water, then, described radiation crosslinking gel is immersed in acid or the acid solution to obtain modified gel.
8. one kind prepares the method that its main component is the gel of carboxymethyl cellulose alkali metal salt (CMC), by acid or acid solution and water-insoluble metallic compound are mixed with gelation CMC with CMC.
9. the described according to Claim 8 method for preparing gel, wherein, the weight of described CMC is less than 65% of the parent material gross weight.
10. the described according to Claim 8 method for preparing gel, wherein, described acid or acid solution are hydrochloric acid or hydrochloric acid soln, and described water-insoluble metallic compound is an aluminum oxide.
11. a gel, it comprises carboxymethyl cellulose alkali metal salt (CMC), acid or acid solution and water-insoluble metallic compound as main component.
12. gel according to claim 11, wherein, described acid or acid solution are hydrochloric acid or hydrochloric acid soln, and described water-insoluble metallic compound is an aluminum oxide.
13. a method for preparing the gel that comprises carboxymethyl cellulose alkali metal salt (CMC) is by mixing acid or acid solution and organic enhancing body compound with CMC.
14. the method for preparing gel according to claim 13, wherein, the content of CMC compares the 3%-64% for the gross weight of the mixture that comprises CMC, acid solution and organic enhancing body.
15. the method for preparing gel according to claim 13 wherein, joins hydrochloric acid or hydrochloric acid soln among the CMC as described acid or acid solution.
16. the method for preparing gel according to claim 13, wherein said organic enhancing body is one or more organic compound that are selected from the group that comprises Microcrystalline Cellulose, pectin, alginic acid, gelling gum, cm-chitosan, polyethylene and poly(lactic acid).
17. a gel, it comprises carboxymethyl cellulose alkali metal salt, acid or acid solution and organic enhancing body as main component.
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| JP2006250947A JP4288618B2 (en) | 2006-09-15 | 2006-09-15 | Method for producing carboxymethylcellulose gel |
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| JP2006250947 | 2006-09-15 | ||
| JP2007070145 | 2007-03-19 | ||
| JP2007070145A JP2008230996A (en) | 2007-03-19 | 2007-03-19 | Method for producing gel containing carboxymethylcellulose as main component, and gel |
| JP2007-070145 | 2007-03-19 | ||
| JP2007-188845 | 2007-07-19 | ||
| JP2007188845 | 2007-07-19 | ||
| JP2007188845A JP5030219B2 (en) | 2007-07-19 | 2007-07-19 | Process for producing gel of carboxymethylcellulose alkali salt and gel of carboxymethylcellulose alkali salt obtained thereby |
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| CN105011343A (en) * | 2015-05-27 | 2015-11-04 | 青岛农业大学 | Intestinal tract targeting and pH-sensitive complex coacervation microcapsule transmission system and preparation method and application thereof |
| CN113150324A (en) * | 2021-04-13 | 2021-07-23 | 华南理工大学 | TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel and preparation method and application thereof |
| CN114921401A (en) * | 2022-05-24 | 2022-08-19 | 灵知蓝诺(北京)生物技术有限公司 | Method for extracting cells from mucus based on liquid-phase molecular sieve |
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| JP5429527B2 (en) * | 2008-04-21 | 2014-02-26 | 眞知子 瀧上 | Method for producing gel of carboxymethylcellulose alkali metal salt |
| WO2010122687A1 (en) | 2009-04-20 | 2010-10-28 | 独立行政法人日本原子力研究開発機構 | Method for producing gel of carboxymethyl cellulose alkali metal salt |
| ES2626116T3 (en) * | 2008-11-18 | 2017-07-24 | Gelesis Llc | Methods and compositions for weight control and for improving glycemic control |
| JP2010121028A (en) * | 2008-11-19 | 2010-06-03 | Ina Food Industry Co Ltd | Modified xanthan gum, modified gum arabic, and modified tamarind seed gum, and method for cross-linking xanthan gum, gum arabic, and tamarind seed gum |
| CN103025763B (en) * | 2010-05-21 | 2015-06-24 | 高木千代美 | Dry cellulose gel and process for producing same |
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| JP6726109B2 (en) | 2014-06-20 | 2020-07-22 | ジェレシス，エルエルシー | Composition for treating overweight or obesity |
| EP3250612B1 (en) * | 2015-01-29 | 2020-12-02 | Gelesis LLC | Method for producing hydrogels coupling high elastic modulus and absorbance |
| CN110551300A (en) * | 2018-05-30 | 2019-12-10 | 华南理工大学 | Water-resistant transparent cellulose-based film and preparation method thereof |
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| CN114651038A (en) * | 2020-06-18 | 2022-06-21 | 国立研究开发法人日本原子力研究开发机构 | Gel, porous body and method for producing gel or porous body |
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| KR100730527B1 (en) * | 1999-02-19 | 2007-06-20 | 덴끼 가가꾸 고교 가부시키가이샤 | Hyaluronic acid gel composition, process for producing the same, and medical material containing the same |
| ITTO20040918A1 (en) * | 2004-12-29 | 2005-03-29 | Luigi Ambrosio | POLYMERIC HYDROGEL BIODEGRADABLE ABSORBERS AND PROCEDURE FOR THEIR PREPARATION |
| CN1803185A (en) * | 2005-01-12 | 2006-07-19 | 中南大学湘雅二医院 | Compound zedoary turmeric oil gelata and its preparing method |
| CN100340231C (en) * | 2005-10-18 | 2007-10-03 | 合肥华威药业有限责任公司 | Itch eliminatin gel and its preparing method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105011343A (en) * | 2015-05-27 | 2015-11-04 | 青岛农业大学 | Intestinal tract targeting and pH-sensitive complex coacervation microcapsule transmission system and preparation method and application thereof |
| CN105011343B (en) * | 2015-05-27 | 2018-01-19 | 青岛农业大学 | A kind of intestinal-specific pH sensitiveness condenses microcapsule delivery system and preparation method and application again |
| CN113150324A (en) * | 2021-04-13 | 2021-07-23 | 华南理工大学 | TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel and preparation method and application thereof |
| CN114921401A (en) * | 2022-05-24 | 2022-08-19 | 灵知蓝诺(北京)生物技术有限公司 | Method for extracting cells from mucus based on liquid-phase molecular sieve |
| CN114921401B (en) * | 2022-05-24 | 2023-07-18 | 灵知蓝诺(北京)生物技术有限公司 | Method for extracting cells from mucus based on liquid phase molecular sieve |
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