CN1762574A - Synthesis of high molecular and active carbon porous microsphere, its preparation method and use - Google Patents
Synthesis of high molecular and active carbon porous microsphere, its preparation method and use Download PDFInfo
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- CN1762574A CN1762574A CN 200510021774 CN200510021774A CN1762574A CN 1762574 A CN1762574 A CN 1762574A CN 200510021774 CN200510021774 CN 200510021774 CN 200510021774 A CN200510021774 A CN 200510021774A CN 1762574 A CN1762574 A CN 1762574A
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Abstract
The disclosed synthesized macromolecular and active carbon hybridized porous microballoon is characteristic in that: preparing macromolecular liquid with 5~15 macromolecule, 0.01~10 additive, and 40~90 solvent; adding 5~50 powder active carbon into said liquid to obtain mixed suspending liquid; injecting said liquid into nonsolvent of macromolecular compound, stirring to prepare the final product. Wherein, the diameter is 2~4mm, the porosity is 15~90%, and active carbon takes up 25~90%. The adsorption column made from this product can remove hormone toxin, liver and heavy metal ion with removal quantity as 2~80mg/g, 5~50mg/g and 1~30mg/g, respectively.
Description
Technical field
The present invention relates to a kind of synthetic high polymer and active carbon porous microsphere and its production and use.Belong to the modification field of functional materials.
Background technology
Active carbon is a kind of wide spectrum adsorbent, because its great specific area makes it all have good removing effect to multiple material.Yet active carbon generally is very tiny powdered substance, when directly using with certain difficulty is arranged separating of liquid.Especially be applied to blood perfusion, or when handling beverage, drinking water, can directly having influence on the quality and the quantity of processing, even bring some negative effects.Therefore activated carbon surface all wraps up a skim when blood perfusion, improves the blood compatibility of material, prevents the stripping of the little molecule particle of solubility simultaneously.Aspect the removing environmental hormone, active carbon also has its very big advantage.
" environmental hormone " speech is to be reported by U.S.'s " Boston environment " in 1996 in institute's work " bereft future " book such as reporter Anda Ma Nuosiji at first to put forward.Environmental hormone is Environmental Hormone again, and hormone confuses element, or element is confused in endocrine.The existence of Environmental Hormone material in food, water and soil earth become worldwide problem.Environmental Hormone will be had an effect under extremely low concentration.Environmental Hormone will send error message after entering receptors bind in human body and the cell in vivo, thereby destroys the normal metabolism of organism, secretion and reproduction function.
The removing of Environmental Hormone material can be passed through the diverse ways selective clearing.Adopting the method removing Environmental Hormone of absorption is a kind of very convenient and effective method.Ultraviolet ray irradiation makes duplex DNA crosslinked, this insoluble DNA film can selective clearing have planar structure the Environmental Hormone material (people such as M.Yamadad, Environ.Sci.Technol., 2001,36:949).Hydrophobic dimethyl silicone polymer film also selective absorption Environmental Hormone material (people such as B.O.Yoon, J.Membr.Sci., 2003,213:137).The present inventor applied in earlier stage DNA modified high-molecular microballoon (application number: 200310110854.7) and the patent of polysulfones porous microsphere (application number: 200310110855.1), the porous microsphere of preparation can be used for removing environmental toxin.Yet DNA is very expensive, and dimethyl silicone polymer film and polysulfones porous microsphere adsorption effect are not good enough.It is also bad directly to remove effect with activated carbon granule, and with needing centrifugation to go out active carbon powder after the active carbon powder absorption.The patent of invention of domestic relevant active carbon is a lot, but majority is the preparation of active carbon and the patent of regeneration aspect, having only only a few is (97106433.4 of preparation active carbon compound adsorbent, 00119588.3,03810315.X), do not see the report that synthetic high polymer and absorbent charcoal composite material are arranged, more do not relate to the removing of environmental hormone.
Summary of the invention
The objective of the invention is provides a kind of synthetic high polymer and active carbon porous microsphere and manufacture method and purposes at the deficiencies in the prior art, be characterized in that synthetic high polymer and active carbon prepare porous microsphere by blend hydridization method and the technology that is separated, can remove the Environmental Hormone toxin, flesh liver and heavy metal ion.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient of synthetic high polymer-active carbon hybrid microspheres contains: synthetic high polymer is 5～15 weight portions, is preferably the 8-12 weight portion; Active carbon is 5～50 weight portions, is preferably the 10-25 weight portion.
The manufacture method of synthetic high polymer-active carbon hybrid microspheres:
1. the preparation of solution
With 5～15 parts of synthetic high polymers, 40～90 parts of solvents and 0.01～10 part of three component of additive are put into container, under agitation in 75～95 ℃ of dissolvings of temperature 2～24 hours, make Polymer Solution.Again active carbon is slowly joined in the Polymer Solution for 5～50 parts and mix, prepare uniform synthetic high polymer and active carbon mixing suspension.
2. the preparation of microballoon
With above-mentioned macromolecule mixing suspension, inject high molecular non-solvent water, and stir, the preparation porous microsphere.Its diameter is 2～4mm, and porosity is 15～90%, and the ratio of active carbon in the blending and modifying microballoon is 25%～90%.
Wherein synthetic high polymer is any in polysulfones, polyether sulfone, polyacrylonitrile or the polyurethane; Solvent is any in N-methyl-pyrrolidones, dimethylacetylamide or the dimethyl formamide; Additive is any in polyethylene glycol, polyvinylpyrrolidone or the propane diols.
The purposes of synthetic high polymer provided by the invention and active carbon porous microsphere
Synthetic high polymer-active carbon porous microsphere is directly made adsorption column, can remove flesh liver and heavy metal ion in Environmental Hormone material toxin, the blood.
The present invention has following advantage:
1. with synthesized polymer material and active carbon powder hydridization, prepare porous microsphere, method is simple.
2. synthetic high polymer is fixed active carbon powder, has avoided coming off of active carbon powder; Improved its blood compatibility when being applied to blood perfusion.
3. synthesized polymer material and active carbon porous microsphere are wide to the removing scope of Environmental Hormone material, the clearance rate height.
4. synthesized polymer material and active carbon porous microsphere can be removed the flesh hepatotoxin in the blood effectively.
5. synthesized polymer material and active carbon porous microsphere can be removed heavy metal ion effectively.
The specific embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment:
1. with polyether sulfone 10 grams, polyethylene glycol 1 restrains, and N-methyl pyrrolidone 79 grams add in the container, stir 4 hours for 80 ℃ in temperature, obtain Polymer Solution.Again active carbon powder 10 grams are slowly joined in the Polymer Solution, be mixed with mixing suspension.Injection needle by 1.2mm injects water with above-mentioned mixing suspension, stirs under 100rpm speed.Microsphere diameter is 2.7mm, places in deionized water 24 hours, and changes deionized water for several times, removes residual solvent, makes adsorption column, is 50mg/g to the removing amount of bisphenol-A; Removing amount to the flesh liver is 25mg/g; Removing amount to metal copper ion is 3.5mg/g.
2. with polysulfones 8 grams, polyvinylpyrrolidone 0.5 restrains, and dimethyl formamide 79.5 grams add in the container, stir 6 hours for 75 ℃ in temperature, obtain Polymer Solution.Active carbon powder 12 grams are slowly joined in the Polymer Solution, be mixed with mixing suspension.Injection needle by 1.2mm injects water with above-mentioned mixing suspension, stirs under 100rpm speed.Microsphere diameter is 2.8mm, places 24 hours in deionized water, and changes deionized water for several times, removes residual solvent, makes adsorption column, and Pyrogentisinic Acid's removing amount is 9mg/g; Removing amount to the flesh liver is 29mg/g; Removing amount to metal copper ion is 3.8mg/g.
3. with polyether sulfone 7 grams, propane diols 4 restrains, and dimethylacetylamide 68 grams add in the container, stir 8 hours for 85 ℃ in temperature, obtain Polymer Solution.Active carbon powder 21 grams are slowly joined in the Polymer Solution, be mixed with mixing suspension.Injection needle by 1.2mm injects water with above-mentioned mixing suspension, stirs under 100rpm speed.Microsphere diameter is 2.8mm, places in deionized water 24 hours, and changes deionized water for several times, removes residual solvent, makes adsorption column, is 55mg/g to the removing amount of bisphenol-A; Removing amount to the flesh liver is 30mg/g; Removing amount to metal copper ion is 3.8mg/g.
4. with polysulfones 12 grams, propane diols 3 restrains, and dimethylacetylamide 73 grams add in the container, stirs 12 hours the acquisition Polymer Solution for 90 ℃ down in temperature.Again active carbon powder 12 grams are slowly joined in the Polymer Solution, be mixed with mixing suspension.Injection needle by 1.2mm injects water with above-mentioned mixing suspension, stirs under 100rpm speed.Microsphere diameter is 2.7mm, places in deionized water 24 hours, and changes deionized water for several times, removes residual solvent, makes adsorption column, is 25mg/g to the removing amount of dibenzofuran; Removing amount to diethylstilbestrol is 20mg/g; Removing amount to the flesh liver is 24mg/g; Removing amount to metal copper ion is 3.2mg/g.
5. with polyacrylonitrile 10 grams, polyethylene glycol 0.5 restrains, and dimethylacetylamide 79.5 grams add in the container, stirs 10 hours the acquisition Polymer Solution for 80 ℃ down in temperature.Again active carbon powder 10 grams are slowly joined in the Polymer Solution, be mixed with mixing suspension.Injection needle by 1.2mm injects water with above-mentioned mixing suspension, stirs under 100rpm speed.Microsphere diameter is 2.7mm, places in deionized water 24 hours, and changes deionized water for several times, removes residual solvent, makes adsorption column, is 45mg/g to the removing amount of bisphenol-A; Removing amount to the flesh liver is 21mg/g; Removing amount to metal copper ion is 3.1mg/g.
6. with polyurethane 12 grams, propane diols 0.2 restrains, and dimethylacetylamide 75.8 grams add in the container, stirs 14 hours the acquisition Polymer Solution for 85 ℃ down in temperature.Again active carbon powder 12 grams are slowly joined in the Polymer Solution, be mixed with mixing suspension.Injection needle by 1.2mm injects water with above-mentioned mixing suspension, stirs under 100rpm speed.Microsphere diameter is 2.7mm, places in deionized water 24 hours, and changes deionized water for several times, removes residual solvent, makes adsorption column, is 23mg/g to the removing amount of dibenzofuran; Removing amount to diethylstilbestrol is 18mg/g; Removing amount to the flesh liver is 24mg/g; Removing amount to metal copper ion is 3.1mg/g.
Application example:
1. the preparation of adsorption column is filled in the separation adsorption column with microballoon, and volume can be adjusted as required, preparation microballoon adsorption column.
2. synthetic high polymer-active carbon porous microsphere is used to adsorb the Environmental Hormone material.Clearance rate (with the milligram number of porous microsphere follower ring border hormone material) to the Environmental Hormone material is 2～80mg/g, sees table 1 for details.
3. synthetic high polymer-active carbon porous microsphere is used to adsorb the flesh liver.Clearance rate (with the milligram number of every gram synthetic high polymer-active carbon hybrid microspheres absorption Environmental Hormone material) to the flesh liver is 5～50mg/g.
4. synthetic high polymer-active carbon porous microsphere is used to remove heavy metal ion.Clearance rate (every gram contains the milligram number of macromolecule-charcoal absorption heavy metal ion) to heavy metal ion is 1～30mg/g, sees table 2 for details.
Table 1 synthetic high polymer-active carbon porous microsphere is to the clearance rate of component environment hormone material
| Environmental Hormone material Chinese | Environmental Hormone material english abbreviation | Clearance rate (mg/g) |
| Biphenyl dibenzofuran phenol hexichol-p-two dislikes pod bisphenol-A diethylstilbestrol | BP DBF PHE DBD BPA DES | 12～50 12～40 2-12 3～35 15～80 3～30 |
Annotate: clearance rate is the milligram number of the adsorbed Environmental Hormone material of every gram hybrid microspheres.
Table 2 synthetic high polymer-active carbon porous microsphere is to the clearance rate of part heavy metal ion
| Metal ion | Clearance rate (mg/g) |
| Zn 2+ Cu 2+ Pb 2+ Fe 3+ | 1～8 1～9 3～30 1～8 |
Annotate: clearance rate is the milligram number of the adsorbed heavy metal ion of every gram hybrid microspheres.
Claims (8)
1. synthetic high polymer and active carbon porous microsphere is characterized in that the recipe ingredient of this porous microsphere contains: synthetic high polymer 5～15 weight portions, active carbon 5～50 weight portions.
2. according to described synthetic high polymer of claim 1 and active carbon porous microsphere, it is characterized in that synthetic high polymer is 8～12 weight portions, active carbon is 10～25 weight portions.
3. according to the preparation method of claim 1 or 2 described synthetic high polymers and active carbon porous microsphere, it is characterized in that this method contains following steps:
(1) preparation of solution
With synthetic high polymer 5～15 weight portions, solvent 40～90 weight portions and additive 0.01～10 weight portion three components are put into container and are made Polymer Solution; Again active carbon 5～50 weight portions are joined in the Polymer Solution, stir, make synthetic high polymer and active carbon mixing suspension.
(2) preparation of microballoon
With above-mentioned synthetic high polymer and active carbon mixing suspension, inject high molecular non-solvent, stir, make porous microsphere.
4. according to the preparation method of described synthetic high polymer of claim 3 and active carbon porous microsphere, it is characterized in that solvent is any in N-methyl pyrrolidone, dimethylacetylamide or the dimethyl formamide.
5. according to the preparation method of described synthetic high polymer of claim 3 and active carbon porous microsphere, it is characterized in that additive is a polyethylene glycol, any in polyvinylpyrrolidone or the propane diols.
6. according to the preparation method of described synthetic high polymer of claim 3 and active carbon porous microsphere, temperature is 75～95 ℃ when it is characterized in that Polymer Solution prepares, dissolution time 2～24 hours.
7. according to the preparation method of described synthetic high polymer of claim 3 and active carbon porous microsphere, the diameter that it is characterized in that porous microsphere is 2～4mm, and porosity is 15～90%, and the ratio of active carbon in the blending and modifying microballoon is 25%～90%.
8. according to the purposes of described synthetic high polymer of claim 1 and active carbon porous microsphere, it is characterized in that this porous microsphere makes adsorption column, can remove Environmental Hormone toxin, flesh liver and heavy metal ion, the removing amount is respectively 2～80mg/g, 5～50mg/g and 1～30mg/g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219367B (en) * | 2007-09-30 | 2010-05-19 | 四川大学 | Amino acid modified montmorillonite-synthesized polymer hybridisation microsphere, preparation method and application thereof |
| CN108585101A (en) * | 2017-10-27 | 2018-09-28 | 卢伟 | A kind of recovery method of the multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization |
| CN109692371A (en) * | 2019-01-28 | 2019-04-30 | 四川大学 | It is a kind of from anticoagulant double-layer active carbon blood perfusion device and blood perfusion method |
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2005
- 2005-09-29 CN CN 200510021774 patent/CN1762574A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219367B (en) * | 2007-09-30 | 2010-05-19 | 四川大学 | Amino acid modified montmorillonite-synthesized polymer hybridisation microsphere, preparation method and application thereof |
| CN108585101A (en) * | 2017-10-27 | 2018-09-28 | 卢伟 | A kind of recovery method of the multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization |
| CN108585101B (en) * | 2017-10-27 | 2020-12-11 | 新沂市锡沂高新材料产业技术研究院有限公司 | Recovery method of inorganic material hybridized porous biomass microspheres for heavy metal sewage treatment |
| CN109692371A (en) * | 2019-01-28 | 2019-04-30 | 四川大学 | It is a kind of from anticoagulant double-layer active carbon blood perfusion device and blood perfusion method |
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