CN101347127A - Novel surrounding purifying material as well as preparation and use thereof - Google Patents
Novel surrounding purifying material as well as preparation and use thereof Download PDFInfo
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- CN101347127A CN101347127A CNA2008100408301A CN200810040830A CN101347127A CN 101347127 A CN101347127 A CN 101347127A CN A2008100408301 A CNA2008100408301 A CN A2008100408301A CN 200810040830 A CN200810040830 A CN 200810040830A CN 101347127 A CN101347127 A CN 101347127A
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Abstract
The present invention discloses an environmental purification material. The environmental purification material contains chitosan rare earth/transitional metal complex nano-particles generated by complexation of chitosan or chitosan derivative, rare earth ion and transitional metal ion; the diameter of the nano-particle is 10 to 100mm. The present invention is prepared by taking chitosan or chitosan derivative as the basic material, loading and bonding rare earth ion and transitional metal ion with bactericidal activity on chitosan or chitosan derivative by acidification treatment and stirring. The material of the present invention has the advantages of wide bactericidal spectrum, strong antibacterial ability, long antibacterial effect, stable antibacterial performance and no toxicity to human body. In addition, with low cost, abundant raw materials and being degradable, the material of the present invention is an environment-friendly environment purification material, which can be applied in the field of packaging material, architectural coating, fiber material, refreshing membrane, sports articles, plastics, ceramics, public sanitation and daily necessities.
Description
Technical field
The present invention relates to a kind of surrounding purifying material and its production and application, specifically, relate to a kind of shitosan rare earth/transition metal complex that generates by shitosan or chitosan derivatives, rare earth ion and transition metal ions complexing and its production and application.
Background technology
Environment and health problem are the significant problems of contemporary mankind's common concern.Again and again take place in the world wide to cause human death because of the diseases such as cholera, pneumonia, malaria, tuberculosis and hepatitis that comprise that bacterial infection causes, startling.The surprise attack of SARS virus in 2003, in recent years enterovirus EV 71 catch (hand-foot-and-mouth disease) more make people be alerted to bacterium, virus fearful property and harmfulness thereof.Therefore, the growth and the breeding of control of applied environment scavenging material and elimination noxious bacteria have become the important topic in the sciemtifec and technical sphere.Development is lasting, efficient, low toxicity, degradable surrounding purifying material, and the improvement of environment and the raising of health of people level are had crucial meaning.
The core technology of surrounding purifying material is the research and development of antibacterial agent, and traditional antibacterial agent has inorganic antiseptic, organic antibacterial agent and natural antibacterial agent etc.Inorganic antiseptic has advantages such as safety, warm tolerance, persistence, and it generally contains metal cation component and inorganic carriers such as silver, zinc, copper, and is antibiotic long-lasting to improve by slow releasing function.The organic antibacterial agent antimicrbial power is strong, antibiotic rapidly but have shortcomings such as poor heat resistance, facile hydrolysis, persistence difference, and part also has certain toxicity; The natural antimicrobial agent warm tolerance is relatively poor, and range of application is narrower.Therefore existing single type antibacterial agent is difficult to satisfy the demand in market, and develop novel complex antimicrobials and more and more caused people's attention, thus realization broad-spectrum antiseptic truly.
Shitosan is the product of chitin deacetylase base, and chitin is a kind of natural macromolecule amylose, is to be only second to cellulosic second largest class natural polymer, and China's output is big, and price is low, has no side effect, and has excellent biological compatibility, can turn waste into wealth.The utilization of shitosan in aspects such as every field such as chemical industry, environmental protection in recent years is subjected to very big attention, and the report of wherein relevant shitosan and polymer anti-microbial property thereof is more, thinks that shitosan not only has the natural antibacterial performance, and has a broad antifungal spectrum.Rare earth is China's high yield mineral, owing to self particular structure characteristics and physico chemical property, also has anti-microbial property.How to utilize the synergetic antibacterial effect synthetic antimicrobial stability and the long-lasting surrounding purifying material of shitosan, rare earth, transition metal, yet there are no relevant report.
Summary of the invention
One of technical problem to be solved by this invention provides a kind of surrounding purifying material, with overcome above-mentioned existing in prior technology cost costliness, facile hydrolysis, persistence poor, certain toxicity and the narrower defective of range of application arranged.
Two of technical problem to be solved by this invention provides a kind of preparation method of surrounding purifying material of simple to operate, with low cost, suitable suitability for industrialized production.
Three of technical problem to be solved by this invention provides the application of described surrounding purifying material.
For achieving the above object, the technical solution used in the present invention is as follows:
Surrounding purifying material of the present invention is made up of the shitosan rare earth/transition metal complex nano particle that shitosan or chitosan derivatives, rare earth ion and transition metal ions complexing generate, and the particle diameter of nano particle is 10～100nm.
Described shitosan rare earth/transition metal complex middle rare earth ion accounts for 1～40%, and transition metal ions accounts for 1%～10%, and shitosan or chitosan derivatives account for 50%～98%, and described ratio is weight percentage.
The preferred La of described rare earth ion
3+, Ce
4+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+, Y
3+In one or more.
The preferred Ag of described transition metal ions
+, Cu
2+, Zn
2+In one or more.
Described shitosan preferably refining shitosan, food-grade shitosan or high density shitosan, preferred hydroxypropyl chitosan of chitosan derivatives or CMC.
The preparation method of surrounding purifying material of the present invention comprises the steps:
A) at first take by weighing certain amount of chitosan or chitosan derivatives,, be diluted to pH value of solution with a certain amount of water then and be 3～7 with the diluted acid dissolving, stand-by;
B) ratio that takes by weighing respectively with the amount of substance of shitosan or chitosan derivatives is the rare earth compound of (1: 10)～(10: 1), and with the ratio of the amount of substance of rare earth compound be the transistion metal compound of (3: 1)～(1: 3), be made into the rare earth compound solution of 0.01～1.50mol/L and the transistion metal compound solution of 0.005～1.00mol/L respectively;
C) rare earth compound solution and the transistion metal compound solution with the step b) preparation slowly is added drop-wise in the solution of step a) preparation simultaneously, and rate of addition is controlled at 60～80 droplets/minute;
D) at 15～40 ℃, stirring reaction 2～8 hours;
E) reaction finishes, regulator solution pH to 5～8, and the complexing product is separated out with the flocculent deposit form, filters, and uses the distilled water wash filter cake;
F) with filter cake 30～80 ℃ of vacuum dryings 3～10 hours, grind, promptly get surrounding purifying material of the present invention.
The acetum of the diluted acid preferred 1% of above-mentioned steps in a).
Above-mentioned steps b) preferred rare earth nitrades of the rare earth compound in or rare-earth salts hydrochlorate, the preferred transition metal nitrate of transistion metal compound.
Above-mentioned steps d) the preferred 400～1200r/min of the mixing speed in.
Surrounding purifying material of the present invention is to be used for preparing one or more the surrounding purifying material that suppresses Escherichia coli, staphylococcus aureus, bacillus wax, Bacillus megatherium and Candida albicans.
Compared with prior art, beneficial effect of the present invention is as follows:
1) surrounding purifying material of the present invention has good chemical stability and heat endurance, and durability is strong, can use at normal temperatures, storage and transport;
2) surrounding purifying material of the present invention is with low cost, and the abundant and almost non-toxic property of raw material resources, degradable are environmentally friendly;
3) preparation method of surrounding purifying material of the present invention has simple to operately, is suitable for the advantage of suitability for industrialized production;
4) sensitive bacteria of surrounding purifying material of the present invention spectrum is wide, comprise important human pathogens such as Escherichia coli, staphylococcus aureus, bacillus wax, Bacillus megatherium, Candida albicans, and fungistatic effect is obvious, and inhibition zone diameter can reach 22mm, and minimal inhibitory concentration is less than 200mg/L.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the prepared surrounding purifying material of embodiment 1;
Fig. 2 is the prepared surrounding purifying material of embodiment 1 and forms part, the infrared spectrum that records with the KBr pressed disc method;
Fig. 3 is the antibacterial ring sheet of surrounding purifying material of the present invention to staphylococcus aureus.
Embodiment
The present invention is described in further detail and completely below in conjunction with embodiment:
Embodiment 1
A) at first take by weighing the refining shitosan of 1.50mmol,, add entry then and be diluted to pH value of solution and be 4～5 with the acetum dissolving of 40mL 1%, stand-by;
B) taking by weighing ratio with the amount of substance of shitosan is 10: 1 rare earth compound, and with the ratio of the amount of substance of rare earth compound be 2: 3 transistion metal compound, be made into the rare earth compound solution of 1.50mol/L and the transistion metal compound solution of 0.75mol/L respectively;
C) rare earth compound solution and the transistion metal compound solution with the step b) preparation slowly is added drop-wise in the solution of step a) preparation simultaneously, and rate of addition is controlled at 60～80 droplets/minute;
D) at 15 ℃, stirring reaction 8 hours, mixing speed is controlled at 400r/min;
E) reaction finishes, regulator solution pH to 7～8, and the complexing product is separated out with the flocculent deposit form, filters, and uses the distilled water wash filter cake;
F) with filter cake 30 ℃ of vacuum dryings 10 hours, grind, promptly get surrounding purifying material of the present invention.
Above-mentioned steps b) rare earth compound in is commercially available ammonium ceric nitrate, and transistion metal compound is commercially available silver nitrate.
Fig. 1 is the transmission electron microscope photo of the prepared surrounding purifying material of present embodiment, and visible prepared surrounding purifying material is made up of nano particle, and the particle diameter of nano particle is 10～100nm.
Fig. 2 is the prepared surrounding purifying material of present embodiment and forms the infrared spectrum that part records with the KBr pressed disc method, spectral line is followed successively by the infrared line of shitosan, shitosan cerium/silver complex, silver nitrate, ammonium ceric nitrate from top to bottom among the figure, as seen shitosan cerium/silver complex has tangible peak shift and new peak to form with respect to part, complex ion, illustrates that prepared surrounding purifying material is the shitosan rare earth/transition metal complex that is generated by shitosan, rare earth ion and transition metal ions complexing.
The surrounding purifying material middle rare earth ion (Ce that present embodiment is prepared
4+) account for 32.45%, transition metal ions (Ag
+) accounting for 9.31%, shitosan accounts for 58.24%, and described ratio is weight percentage.
Embodiment 2
A) at first take by weighing 2.00mmol food-grade shitosan,, add entry then and be diluted to pH value of solution and be 3～4 with the dissolving of the acetum of 80mL 1%, stand-by;
B) taking by weighing ratio with the amount of substance of shitosan respectively is 5: 1 rare earth compound, and with the ratio of the amount of substance of rare earth compound be 2: 1 transistion metal compound, be made into the rare earth compound solution of 1.00mol/L and the transistion metal compound solution of 0.5mol/L respectively;
C) rare earth compound solution and the transistion metal compound solution with the step b) preparation slowly is added drop-wise in the solution of step a) preparation simultaneously, and rate of addition is controlled at 60～80 droplets/minute;
D) at 25 ℃, stirring reaction 6 hours, mixing speed is controlled at 600r/min;
E) reaction finishes, regulator solution pH to 6～8, and the complexing product is separated out with the flocculent deposit form, filters, and uses the distilled water wash filter cake;
F) with filter cake 50 ℃ of vacuum dryings 7 hours, grind, promptly get surrounding purifying material of the present invention.
Above-mentioned steps b) rare earth compound in is an ammonium ceric nitrate, and transistion metal compound is a silver nitrate.
The surrounding purifying material middle rare earth ion (Ce that present embodiment is prepared
4+) account for 29.42%, transition metal ions (Ag
+) accounting for 8.67%, shitosan accounts for 61.91%, and described ratio is weight percentage.
A) at first take by weighing 1.00mmol high density shitosan,, add entry then and be diluted to pH value of solution and be 4～6 with the dissolving of the acetum of 80mL 1%, stand-by;
B) taking by weighing ratio with the amount of substance of shitosan respectively is 1: 1 rare earth compound, and with the ratio of the amount of substance of rare earth compound be 1: 1 transistion metal compound, be made into the rare earth compound solution of 0.1mol/L and the transistion metal compound solution of 0.05mol/L respectively;
C) rare earth compound solution and the transistion metal compound solution with the step b) preparation slowly is added drop-wise in the solution of step a) preparation simultaneously, and rate of addition is controlled at 60～80 droplets/minute;
D) at 30 ℃, stirring reaction 4 hours, mixing speed is controlled at 800r/min;
E) reaction finishes, regulator solution pH to 7～8, and the complexing product is separated out with the flocculent deposit form, filters, and uses the distilled water wash filter cake;
F) with filter cake 80 ℃ of vacuum dryings 3 hours, grind, promptly get surrounding purifying material of the present invention.
Above-mentioned steps b) rare earth compound in is an ammonium ceric nitrate, and transistion metal compound is a silver nitrate.
The surrounding purifying material middle rare earth ion (Ce that present embodiment is prepared
4+) account for 17.68%, transition metal ions (Ag
+) accounting for 3.79%, shitosan accounts for 78.53%, and described ratio is weight percentage.
A) at first take by weighing the 0.50mmol hydroxypropyl chitosan,, add entry then and be diluted to pH value of solution and be 4～5 with the dissolving of the acetum of 40mL 1%, stand-by;
B) taking by weighing ratio with the amount of substance of chitosan derivatives respectively is 1: 5 rare earth compound, and with the ratio of the amount of substance of rare earth compound be 1: 2 transistion metal compound, be made into the rare earth compound solution of 0.01mol/L and the transistion metal compound solution of 0.005mol/L respectively;
C) rare earth compound solution and the transistion metal compound solution with the step b) preparation slowly is added drop-wise in the solution of step a) preparation simultaneously, and rate of addition is controlled at 60～80 droplets/minute;
D) at 40 ℃, stirring reaction 2 hours, mixing speed is controlled at 1200r/min;
E) reaction finishes, regulator solution pH to 7～8, and the complexing product is separated out with the flocculent deposit form, filters, and uses the distilled water wash filter cake;
F) with filter cake 60 ℃ of vacuum dryings 6 hours, grind, promptly get surrounding purifying material of the present invention.
Above-mentioned steps b) rare earth compound in is an ammonium ceric nitrate, and transistion metal compound is a silver nitrate.
The surrounding purifying material middle rare earth ion (Ce that present embodiment is prepared
4+) account for 8.45%, transition metal ions (Ag
+) accounting for 1.16%, chitosan derivatives accounts for 90.39%, and described ratio is weight percentage.
A) at first take by weighing the 2.00mmol CMC,, add entry then and be diluted to pH value of solution and be 3～5 with the dissolving of the acetum of 80mL 1%, stand-by;
B) taking by weighing ratio with the amount of substance of chitosan derivatives respectively is 1: 10 rare earth compound, and with the ratio of the amount of substance of rare earth compound be 1: 3 transistion metal compound, be made into the rare earth compound solution of 0.50mol/L and the transistion metal compound solution of 0.17mol/L respectively;
C) rare earth compound solution and the transistion metal compound solution with the step b) preparation slowly is added drop-wise in the solution of step a) preparation simultaneously, and rate of addition is controlled at 60～80 droplets/minute;
D) at 35 ℃, stirring reaction 5 hours, mixing speed is controlled at 900r/min;
E) reaction finishes, regulator solution pH to 7～8, and the complexing product is separated out with the flocculent deposit form, filters, and uses the distilled water wash filter cake;
F) with filter cake 70 ℃ of vacuum dryings 5 hours, grind, promptly get surrounding purifying material of the present invention.
Above-mentioned steps b) rare earth compound in is an ammonium ceric nitrate, and transistion metal compound is a silver nitrate.
The surrounding purifying material middle rare earth ion (Ce that present embodiment is prepared
4+) account for 25.17%, transition metal ions (Ag
+) accounting for 5.17%, chitosan derivatives accounts for 69.66%, and described ratio is weight percentage.
Embodiment 6
The difference of present embodiment and embodiment 4 is: described transistion metal compound is a copper nitrate.
All the other contents are all described identical with embodiment 4.
The surrounding purifying material middle rare earth ion (Ce that present embodiment is prepared
4+) account for 10.21%, transition metal ions (Cu
2+) accounting for 1.19%, chitosan derivatives accounts for 88.60%, and described ratio is weight percentage.
Embodiment 7
The difference of present embodiment and embodiment 4 is: described transistion metal compound is a zinc nitrate.
All the other contents are all described identical with embodiment 4.
The surrounding purifying material middle rare earth ion (Ce that present embodiment is prepared
4+) account for 9.56%, transition metal ions (Zn
2+) accounting for 1.09%, chitosan derivatives accounts for 89.75%, and described ratio is weight percentage.
Embodiment 8
The difference of present embodiment and embodiment 4 is: described rare earth compound is the rare-earth salts hydrochlorate, is made by rare earth oxide and hydrochloric acid reaction, and wherein, rare earth ion is selected from La
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+, Y
3+In one or more.
All the other contents are all described identical with embodiment 4.
The prepared surrounding purifying material middle rare earth ion of present embodiment accounts for 8.45%～10.21%, transition metal ions (Ag
+) accounting for 1.09%～1.19%, chitosan derivatives accounts for 88.60%～90.39%, and described ratio is weight percentage.
Embodiment 9
Embodiment 1～5 prepared surrounding purifying material is cultivated altogether with Escherichia coli (ATCC8099), staphylococcus aureus (ATCC6538), bacillus wax, Bacillus megatherium or Candida albicans respectively, carried out the test of antibacterial ring and minimal inhibitory concentration.
Said antibacterial ring and minimal inhibitory concentration test method are according to 2.1.8.2 of Ministry of Health of the People's Republic of China 2002 " disinfection technology standard " " antibacterial ring test " and 2.1.8.4 " minimal inhibitory concentration determination test (nutrient broth dilution method) " operation.Wherein used bacterial classification: Escherichia coli (ATCC8099), staphylococcus aureus (ATCC6538), bacillus wax, Bacillus megatherium and Candida albicans are provided by Shanghai Pharmaceutical Inst., Chinese Academy of Sciences.
Fig. 3 is the antibacterial ring sheet of the prepared surrounding purifying material of the foregoing description to staphylococcus aureus, and among the figure: 1. be refining shitosan cerium/silver complex, inhibition zone diameter is 22mm; 2. be food-grade shitosan cerium/silver complex, inhibition zone diameter is 18mm; 3. be high density shitosan cerium/silver complex, inhibition zone diameter is 17mm; 4. be CMC cerium/silver complex, inhibition zone diameter is 21mm; 5. be blank (sterile water).As seen, inhibition zone diameter can reach 22mm all much larger than 7mm.
Table 1 is the minimal inhibitory concentration (MIC) of the prepared surrounding purifying material of the foregoing description.As seen, the MIC value scope of prepared surrounding purifying material is all less than 200mg/L.
According to People's Republic of China's chemical industry standard code: the inhibition zone diameter of compound has been judged to bacteriostasis greater than 7mm, and the big more explanation bacteriostasis of inhibition zone diameter is big more; The minimal inhibitory concentration of compound can be used as antibacterial agent less than 800mg/L and uses, and the more for a short time antibacterial effect that shows of this value is good more.Illustrate that the prepared surrounding purifying material of the present invention has antibacterial action, and antibacterial effect is obvious.
The minimal inhibitory concentration of table 1. complex (MIC:mg/L)
Claims (10)
1. surrounding purifying material, it is characterized in that, described surrounding purifying material is made up of the shitosan rare earth/transition metal complex nano particle that shitosan or chitosan derivatives, rare earth ion and transition metal ions complexing generate, and the particle diameter of nano particle is 10～100nm.
2. surrounding purifying material according to claim 1, it is characterized in that described shitosan rare earth/transition metal complex middle rare earth ion accounts for 1～40%, transition metal ions accounts for 1%～10%, shitosan or chitosan derivatives account for 50%～98%, and described ratio is weight percentage.
3. surrounding purifying material according to claim 1 is characterized in that described rare earth ion is selected from La
3+, Ce
4+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+And Y
3+In one or more.
4. surrounding purifying material according to claim 1 is characterized in that described transition metal ions is selected from Ag
+, Cu
2+And Zn
2+In one or more.
5. surrounding purifying material according to claim 1 is characterized in that, described shitosan is refining shitosan, food-grade shitosan or high density shitosan, and described chitosan derivatives is hydroxypropyl chitosan or CMC.
6. the preparation method of the described surrounding purifying material of claim 1 is characterized in that, described method comprises the steps:
A) at first take by weighing certain amount of chitosan or chitosan derivatives,, be diluted to pH value of solution with a certain amount of water then and be 3～7 with the diluted acid dissolving, stand-by;
B) ratio that takes by weighing respectively with the amount of substance of shitosan or chitosan derivatives is the rare earth compound of (1: 10)～(10: 1), and with the ratio of the amount of substance of rare earth compound be the transistion metal compound of (3: 1)～(1: 3), be made into the rare earth compound solution of 0.01～1.50mol/L and the transistion metal compound solution of 0.005～1.00mol/L respectively;
C) rare earth compound solution and the transistion metal compound solution with the step b) preparation slowly is added drop-wise in the solution of step a) preparation simultaneously, and rate of addition is controlled at 60～80 droplets/minute;
D) at 15～40 ℃, stirring reaction 2～8 hours;
E) reaction finishes, regulator solution pH to 5～8, and the complexing product is separated out with the flocculent deposit form, filters, and uses the distilled water wash filter cake;
F) with filter cake 30～80 ℃ of vacuum dryings 3～10 hours, grind, promptly get surrounding purifying material of the present invention.
7. the preparation method of surrounding purifying material according to claim 6 is characterized in that, the diluted acid in the described step a) is 1% acetum.
8. the preparation method of surrounding purifying material according to claim 6 is characterized in that, the rare earth compound in the described step b) is rare earth nitrades or rare-earth salts hydrochlorate, and transistion metal compound is a transition metal nitrate.
9. the preparation method of surrounding purifying material according to claim 6 is characterized in that, the mixing speed in the described step d) is 400～1200r/min.
10. the application of the described surrounding purifying material of claim 1, it is characterized in that described surrounding purifying material is to be used for preparing one or more the surrounding purifying material that suppresses Escherichia coli, staphylococcus aureus, bacillus wax, Bacillus megatherium and Candida albicans.
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|---|---|---|---|
| CNA2008100408301A CN101347127A (en) | 2008-07-22 | 2008-07-22 | Novel surrounding purifying material as well as preparation and use thereof |
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|---|---|---|---|
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| CN102329438A (en) * | 2011-10-24 | 2012-01-25 | 武汉大学 | Magnetic chitosan/doped rare earth compound particles and preparation method thereof |
| CN102358786A (en) * | 2011-08-29 | 2012-02-22 | 武汉大学 | Magnetic carboxylation chitosan/mixing rare earth composite particle and method for preparing same |
| CN104277124A (en) * | 2014-05-07 | 2015-01-14 | 山东省医疗器械研究所 | Lanthanide rare earth coordinated cellulose medical material and preparation method thereof |
| CN104472537A (en) * | 2014-11-11 | 2015-04-01 | 南京工程学院 | Eggshell-type antibacterial microspheres and preparation method thereof |
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| CN102358786A (en) * | 2011-08-29 | 2012-02-22 | 武汉大学 | Magnetic carboxylation chitosan/mixing rare earth composite particle and method for preparing same |
| CN102329438A (en) * | 2011-10-24 | 2012-01-25 | 武汉大学 | Magnetic chitosan/doped rare earth compound particles and preparation method thereof |
| CN104277124A (en) * | 2014-05-07 | 2015-01-14 | 山东省医疗器械研究所 | Lanthanide rare earth coordinated cellulose medical material and preparation method thereof |
| CN104472537A (en) * | 2014-11-11 | 2015-04-01 | 南京工程学院 | Eggshell-type antibacterial microspheres and preparation method thereof |
| CN107216409A (en) * | 2015-08-27 | 2017-09-29 | 武汉轻工大学 | A kind of preparation method of chitosan L malic acid rare earth compoundings |
| CN105061636B (en) * | 2015-08-27 | 2017-08-29 | 武汉轻工大学 | A kind of preparation method of chitosan citrate rare earth compounding |
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| CN105061636A (en) * | 2015-08-27 | 2015-11-18 | 赵胜军 | Preparation method of chitosan, citric acid and rare earth coordination compound |
| CN107325201A (en) * | 2015-08-27 | 2017-11-07 | 武汉轻工大学 | A kind of preparation method of chitosan salicylic acid rare earth compounding |
| CN107163166B (en) * | 2015-08-27 | 2020-08-14 | 武汉轻工大学 | Preparation method of chitosan-citric acid-rare earth complex |
| CN105696112A (en) * | 2016-03-08 | 2016-06-22 | 安徽微美纳米技术有限公司 | Copper-ion antibacterial socks |
| CN105696112B (en) * | 2016-03-08 | 2017-12-26 | 安徽微美纳米技术有限公司 | A kind of copper ion antibacterial socks |
| CN109023571A (en) * | 2018-08-16 | 2018-12-18 | 江苏华昌织物有限公司 | A kind of composite fibre and its application in rice fly net |
| CN109023571B (en) * | 2018-08-16 | 2021-08-17 | 江苏华昌织物有限公司 | Composite fiber and application thereof in rice insect-proof net |
| CN110812948A (en) * | 2019-10-18 | 2020-02-21 | 东莞市亿茂滤材有限公司 | Multifunctional filtering material and preparation method thereof |
| US11560487B2 (en) | 2020-09-22 | 2023-01-24 | Swimc Llc | Coating compositions containing low molecular weight chitosan composition |
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