CN101088599A - Prepn and product of adsorbing material - Google Patents
Prepn and product of adsorbing material Download PDFInfo
- Publication number
- CN101088599A CN101088599A CN 200610087443 CN200610087443A CN101088599A CN 101088599 A CN101088599 A CN 101088599A CN 200610087443 CN200610087443 CN 200610087443 CN 200610087443 A CN200610087443 A CN 200610087443A CN 101088599 A CN101088599 A CN 101088599A
- Authority
- CN
- China
- Prior art keywords
- reaction
- copolymer
- crosslinking
- homogeneous
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention is process of preparing adsorbing material, which is high cross-linked macroporous adsorption resin prepared with cross-linked macroporous ternary copolymer of polystyrene, vinyl acetate and divinyl benzene as the skeleton and through chloromethylation and additional cross-linking reaction. The adsorbing material is used specially in removing the drug residue in the blood of drug user. Its preparation process includes copolymerization reaction, chloromethylation reaction and additional cross-linking reaction. The product of the present invention is netted high cross-linked macroporous adsorption resin with homogeneous pore distribution.
Description
Technical field that the present invention belongs to
The invention belongs to a kind of is skeleton goes out high crosslinked macroporous absorbent resin through chloromethylation and additive-crosslinking prepared in reaction preparation method and product with the crosslinked macroporous polystyrene of height, vinylacetate, divinylbenzene terpolymer, this product sorbing material is exclusively used in the blood perfusion technique, removes in drug addict's blood and is detained drug materials.
The prior art background
Traditional handicraft selects for use nitrobenzene and zinc dichloride to react, because there is following defective in nitrobenzene: (1) toxicity is big; (2) need the higher reaction temperature that gets, energy resource consumption is big; (3) environmental pollution is more serious; (4) health hazard to operating personnel is big; (5) post processing is very difficult, and solvent load is big; (6) cross-linked network of product resin and crosslinked skewness.Not seeing the product that uses the inventive method to manufacture in addition as yet has clinical practice in the blood perfusion adsorption technology, and the report of succeeing.
The content of invention
The present invention is a kind of method of sorbing material preparation; This sorbing material be a kind of be skeleton with the crosslinked macroporous polystyrene of height, vinylacetate, divinylbenzene terpolymer, through the high crosslinked macroporous absorbent resin that chloromethylation and additive-crosslinking prepared in reaction go out, be exclusively used in to remove in drug addict's blood and be detained drug materials; Preparation method of the present invention comprises: copolyreaction, chloromethylation, additive-crosslinking reaction.
Copolyreaction:
The styrene-content of participating in copolymer reaction is greater than 99.9%, vinylacetate 99%, divinylbenzene content 45%～55% addition is in the degree of cross linking 2%～10%, pore-foaming agent is that toluene and viscosity are the atoleine of 36-40%, addition is a monomer total amount 20%～80%, initator benzoyl peroxide and azobisisobutyronitrile addition are 1%～2% of monomer, and the two ratio is 1: 1; More than constitute oil phase; Water is a deionized water, and wherein adding the two ratio of the pure and mild gelatin of polyethylene of dispersing agent is 0.5: 1, and addition is that 1～2% of water total amount adds sodium chloride 5～10% in addition, and oil is 1: 5～8 with the water ratio; Reaction temperature is 60-80 ℃, 6～8 hours reaction time; 80～95 ℃ of solidification temperatures, 8～12 hours hardening times; Above-mentioned polymerisation is overlapped the terpolymerization reaction that suspends in the reactor at the strap clamp with agitator, thermometer and returned cold radiator cooler, makes crosslinked macroporous copolymer i.e. " Archon ", and its reaction equation is as follows:
Chloromethylation:
With sphere diameter＜1.25mm and＞0.6mm, dilation 3.4～3.7mL/g, it is raw material that water content is not more than 0.5% the above-mentioned Archon of handling well, 1 unit Archon is put into the at room temperature abundant swelling of the chloromethyl ether of using 4-5 unit in the dry reactor 6～8 hours, turn on agitator, the control temperature is no more than 30 ℃, divide three times and add the catalyst zinc chloride, each 30-40 minute at interval, the adding total amount was a 0.5-0.8 unit, then is warmed up to 38-40 ℃, reacted 18-24 hour, make chloromethylated copolymer chlorine ball i.e. " chlorine ball ", its chlorinity is 18-22%, water content≤2%; Its reaction equation is as follows:
Additive-crosslinking is sent out and is answered:
In the reactor of drying, with the abundant swelling 8-12 of the dichloroethanes of 5～6 units hour, then add the catalyst anhydrous ferric trichloride of 1/10-2/10 unit with the chlorine ball of 1 unit, 60-80 ℃ of reaction 8-12 hour, make the high-crosslinking-degree macroporous absorbent resin.Its reaction equation is as follows:
For improving the structure and the serviceability of product, the copolyreaction of the inventive method is also with the polar monomer vinylacetate, acrylonitrile or ethyl acrylate are as the 3rd monomer of styrene-divinylbenzene copolyreaction, addition is 2%～12% of a monomer total amount, the consumption of crosslinking agent divinylbenzene is to select low cross-linking 2%～10% for use, the content 45%～55% of divinylbenzene, the pore-foaming agent consumption is 40% of monomer consumption～1 00%, initator is azodiisobutyronitrile and benzoyl peroxide mixed initiator, the ratio of the two is 0.5～1.0, addition is 1%～2% of a monomer total amount, dispersant is a polyvinyl alcohol, gelatin, with the inorganic salts mixed dispersant, prepare homogeneous cross-linked network macroporous copolymer; Its course of reaction briefly explains accompanying drawing 1 as shown in Figure 1:
Vinyl acetate, styrene, divinylbenzene and pore-foaming agent are mixed, under initator and dispersant effect, produce crosslinked macroporous copolymer, draw homogeneous cross-linked network macroporous copolymer behind process cleaning, extraction, the purifying, i.e. the netted Archon of homogeneous.
Chloromethylation is the netted Archon of homogeneous to be added chloromethyl ether and the catalyst zinc dichloride is reacted, make the netted macro porous crosslinking methyl chloride of homogeneous copolymer, the netted Archon of copolymer homogeneous, chloromethyl ether, zinc dichloride three's reaction ratio is 1: 0.8～4.2: 0.5～0.8, low temperature swelling 6～8 hours, reaction temperature is 36～40 ℃, reaction time is 18～24 hours, makes chlorinty and be 18%～22% chloromethylated copolymer; Its course of reaction as shown in Figure 2, as follows to accompanying drawing 2 brief descriptions: with homogeneous cross-linked network macroporous copolymer, chloromethyl ether, zinc chloride 36～40 ℃ of stirring reactions in reactor, produce the netted macro porous crosslinking chloromethylated copolymer of homogeneous, again through cleaning, extract purifying, promptly obtain netted macro porous crosslinking chloromethylated copolymer, be called for short the netted chlorine ball of homogeneous.
Additive-crosslinking reaction is the chloromethylated copolymer that will handle well in the presence of sweller and reaction dissolvent dichloroethanes, catalyst ferric trichloride, carries out the additive-crosslinking reaction, obtains the crosslinked macroporous absorbent resin of big net equal hole height; The ratio of reactant is: chloromethylated copolymer: dichloroethanes: the ratio of ferric trichloride is 1: 4.5～7.5: 0.12～2.0; Reaction temperature is 60～80 ℃; Reaction time is 8～12 hours; Make the high crosslinked macroporous absorbent resin of equal hole pattern shape; Its course of reaction as shown in Figure 3, and is as follows to accompanying drawing 3 brief description: the netted macro porous crosslinking chloromethylated copolymer of homogeneous, dichloroethanes, anhydrous ferric trichloride in reactor 60～80 ℃; Stirring reaction promptly draws the high crosslinked macroporous absorbent resin of equal hole pattern shape, through cleaning, extracting purifying, draws the high crosslinked macroporous absorbent resin of the equal hole pattern shape of medical grade and is called for short the medical grade polymeric adsorbent.
The chloromethylation catalyst that the inventive method is used can also be: butter of tin, ferric trichloride, alchlor.
The inventive method also comprises the extraction purification reaction at each product:
In A, the synthetic macroporous copolymer that obtains of copolyreaction, contain mechanical admixture, organic molecule, oligomer and mechanical admixture such as little, then adopt hot water wash, acetone extraction or benzinum be extracted into no cured till, alcohol extract, that deionized water is washed till water is limpid, free from extraneous odour, 60 ℃ of oven dry, general＞1.25mm and＜0.6mm sift out as defective pearl ball;
After B, chloromethylated copolymer reaction finish, mother liquor is done with vacuum filtration, filter, with the deionized water flushing,
Dimethoxym ethane with 2～3 times of pearl sphere volumes soaked swelling 4～6 hours, and suction filtration is clean, replaced micro-dimethoxym ethane down with methyl alcohol at last, and the deionized water backwash is to not having the methyl alcohol flavor and using ultraviolet specrophotometer OD
210nm=0.;
After C, additive-crosslinking reaction finish, reactor be cooled off with cold water rapidly, and product water is washed till room temperature, filter; Product soaked 2～8 hours with acetone with acetone drip washing two times again, carried out back flow reaction 4～6 hours in the acetone soln of 0.5～2moL/L HCL, filtered, drained; Add and to contain the methanol solution that alkali concn is 0.5～2moL/L, carried out back flow reaction 4～6 hours, filter, drain, use absolute ethyl alcohol drip washing, at last with alcohol extract to ultraviolet specrophotometer OD
254nm＜0.03.
The inventive method also comprises the material surface chemical modification reaction:
Polymeric adsorbent behind the purifying is dropped in the reactor, carry out the polymeric adsorbent surface chemical modification with 0.2～1.2% collodion ethanolic solution; Then, filtration drying.The collodion modified membrane thickness of resin surface is 3～5 microns.
Nitrobenzene and zinc dichloride that the inventive method does not use traditional handicraft to select for use are reacted, and have overcome every defective that nitrobenzene exists.And the product that the inventive method is manufactured can not swim on the perfusion liquid level than great, is convenient to clinical manipulation; The high crosslinked macroporous absorbent resin of the equal hole pattern shape that the present invention manufactures has good hole structural property, shows to have good adsorption performance and blood compatibility in clinical.
Adopt preparation method of the present invention to make the high crosslinked macroporous absorbent resin of the equal hole pattern shape of medical grade, its various features is:
1. physical property:
1) outward appearance: light yellow or golden yellow opaque spherical particle,
2) particle diameter: 0.6～1.2mm,
3) specific area: 680～820m
2/ g,
4) average pore size: 8.0～20.0nm,
5) pore volume: 0.48～0.56ml/g,
6) porosity: 0.52～0.62%.
2. chemical property (detection of medicine equipment quality supervision and test center, State Food and Drug Administration Jinan)
1) heavy metal ion content: do not detect
2) acid-base value: qualified
3) reducing substances: qualified
4) evaporation residue: do not detect
5) (go into 250～320nm): 0.001 is qualified for UV absorption
3. biological assessment
1) aseptic: qualified
2) no thermal source: qualified
3) hemolysis rate: qualified
4) there is not acute general toxicity: qualified
5) cell-cytotoxic reaction: qualified
6) no intracutaneous IR: qualified
7) no sensitivity response: qualified
8) haemocyte reduces
I. the decrease of platelet rate 2.3%, and standard≤25% is qualified
Ii. the leucocyte slip 10.5%, and standard≤15% is qualified
Iii. the red blood cell slip 7.7%, and standard≤10% is qualified
4. absorption property:
1) the barbital sodium rate of descent 100%, and standard 〉=80% is qualified
2) the VB12 rate of descent 87%, and standard 〉=60% is qualified
3) the morphine rate of descent 84%, and standard 〉=60% is qualified
5. clinical practice:
5 routine drug addicts were through blood perfusion treatment in 2 hours.
1) treatment overall process sign is stable, no abnormal reaction.
2) treatment finishes and carries out excitation experiment, total negative with Allylnoroxymorphone.
3) after the treatment, sign has fine improvement, takes naltrexone and does not have any side reaction.
4) before and after the treatment, blood, the clearance rate of urine morphine is respectively 40%～80% and 60%～85%.
5) before and after the treatment, blood compatibility is good.
Explanation to embodiment of the present invention
In the reaction of implementing each step of the present invention, each scope ratio that participates in the reactant quality that the inventive method provides is relative.Each reaction promptly can be carried out in the scope that provides, and the material that exceeds relative scale when reaction finishes can become reaction residue.The reaction time of each step that the inventive method provides is abundant time of realization response generally speaking, and the operator is the observing response situation of carrying out at any time, timely terminating operation when reflection finishes.
Claims (7)
1, a kind of preparation method of sorbing material, this sorbing material is a kind of high crosslinked macroporous polystyrene, acetic acid
Vinyl acetate, divinylbenzene terpolymer are that skeleton goes out high crosslinked macroporous absorbent resin through chloromethylation and additive-crosslinking prepared in reaction; Be exclusively used in to remove in drug addict's blood and be detained drug materials;
It is characterized in that:
The preparation method comprises: copolyreaction, chloromethylation, additive-crosslinking reaction;
Copolyreaction:
The styrene-content of participating in copolymer reaction is greater than 99.9%, vinylacetate 99%, divinylbenzene content 45%～55% addition is in the degree of cross linking 2%～1 0%, pore-foaming agent is that toluene and atoleine (viscosity is 36-40%) addition are monomer total amount 20%～80%, initator benzoyl peroxide and azobisisobutyronitrile addition are 1%～2% of monomer, and the two ratio is 1: 1; More than constitute oil phase; Water is a deionized water, and wherein adding the two ratio of the pure and mild gelatin of polyethylene of dispersing agent is 0.5: 1, and addition is that 1～2% of water total amount adds sodium chloride 5～10% in addition, and oil is 1: 5～8 with the water ratio; Reaction temperature is 60-80 ℃, 6～8 hours reaction time; 80～95 ℃ of solidification temperatures, 8～12 hours hardening times; Above-mentioned polymerisation is overlapped the terpolymerization reaction that suspends in the reactor at the strap clamp with agitator, thermometer and returned cold radiator cooler, makes crosslinked macroporous copolymer i.e. " Archon ", and its reaction equation is as follows:
Chloromethylation:
With sphere diameter＜1.25mm and＞0.6mm, dilation 3.4～3.7mL/g, it is raw material that water content is not more than 0.5% the above-mentioned Archon of handling well, 1 unit Archon is put into the at room temperature abundant swelling of the chloromethyl ether of using 4-5 unit in the dry reactor 6～8 hours, turn on agitator, the control temperature is no more than 30 ℃, divide three times and add the catalyst zinc chloride, each 30-40 minute at interval, the adding total amount was a 0.5-0.8 unit, then is warmed up to 38-40 ℃, reacted 18-24 hour, make chloromethylated copolymer chlorine ball i.e. " chlorine ball ", its chlorinity is 18-22%, water content≤2%; Its reaction equation is as follows:
Additive-crosslinking is sent out and is answered:
In the reactor of drying, with the abundant swelling 8-12 of the dichloroethanes of 5～6 units hour, then add the catalyst anhydrous ferric trichloride of 1/10-2/10 unit with the chlorine ball of 1 unit, 60-80 ℃ of reaction 8-12 hour, make the high-crosslinking-degree macroporous absorbent resin.Its reaction equation is as follows:
2, the preparation method of sorbing material as claimed in claim 1 is characterized in that:
Copolyreaction is also with the polar monomer vinylacetate, acrylonitrile or ethyl acrylate are as the 3rd monomer of styrene-divinylbenzene copolyreaction, addition is 2%～12% of a monomer total amount, the consumption of crosslinking agent divinylbenzene is to select low cross-linking 2%～10% for use, the content 45%～55% of divinylbenzene, the pore-foaming agent consumption is 40%～100% of a monomer consumption, initator is azodiisobutyronitrile and benzoyl peroxide mixed initiator, the ratio of the two is 0.5～1.0, addition is 1%～2% of a monomer total amount, dispersant is a polyvinyl alcohol, gelatin, with the inorganic salts mixed dispersant, prepare homogeneous cross-linked network macroporous copolymer; Its course of reaction is: vinyl acetate, styrene, divinylbenzene and pore-foaming agent are mixed, under initator and dispersant effect, produce crosslinked macroporous copolymer, draw homogeneous cross-linked network macroporous copolymer behind process cleaning, extraction, the purifying, i.e. the netted Archon of homogeneous:
Chloromethylation is the netted Archon of homogeneous to be added chloromethyl ether and the catalyst zinc dichloride is reacted, make the netted macro porous crosslinking methyl chloride of homogeneous copolymer, the netted Archon of copolymer homogeneous, chloromethyl ether, zinc dichloride three's reaction ratio is 1: 0.8～4.2: 0.5～0.8, low temperature swelling 6～8 hours, reaction temperature is 36～40 ℃, reaction time is 18～24 hours, makes chlorinty and be 18%～22% chloromethylated copolymer; Its course of reaction is: with homogeneous cross-linked network macroporous copolymer, chloromethyl ether, zinc chloride 36～40 ℃ of stirring reactions in reactor, produce the netted macro porous crosslinking chloromethylated copolymer of homogeneous, again through cleaning, extract purifying, promptly obtain netted macro porous crosslinking chloromethylated copolymer, be called for short the netted chlorine ball of homogeneous;
Additive-crosslinking reaction is the chloromethylated copolymer that will handle well in the presence of sweller and reaction dissolvent dichloroethanes, catalyst ferric trichloride, carries out the additive-crosslinking reaction, obtains the crosslinked macroporous absorbent resin of big net equal hole height; The ratio of reactant is: chloromethylated copolymer: dichloroethanes: the ratio of ferric trichloride is 1: 4.5～7.5: 0.12～2.0; Reaction temperature is 60～80 ℃; Reaction time is 8～12 hours; Make the high crosslinked macroporous absorbent resin of equal hole pattern shape; Its course of reaction is: the netted macro porous crosslinking chloromethylated copolymer of homogeneous, dichloroethanes, anhydrous ferric trichloride in reactor 60～80 ℃; Stirring reaction promptly draws the high crosslinked macroporous absorbent resin of equal hole pattern shape, through cleaning, extracting purifying, draws the high crosslinked macroporous absorbent resin of the equal hole pattern shape of medical grade and is called for short the medical grade polymeric adsorbent.
3, the preparation method of sorbing material as claimed in claim 2 is characterized in that the chloromethylation catalyst can also be: butter of tin, ferric trichloride, alchlor.
4, as the preparation method of claim 1 or 2 or 3 described sorbing materials, it is characterized in that wherein extracting purification reaction:
In A, the synthetic macroporous copolymer that obtains of copolyreaction, contain mechanical admixture, organic molecule, oligomer and mechanical admixture such as little, then adopt hot water wash, acetone extraction or benzinum be extracted into no cured till, alcohol extract, that deionized water is washed till water is limpid, free from extraneous odour, 60 ℃ of oven dry, general＞1.25mm and＜0.6mm sift out as defective pearl ball;
After B, chloromethylated copolymer reaction finish, mother liquor is done with vacuum filtration, filter, with the deionized water flushing,
Dimethoxym ethane with 2～3 times of pearl sphere volumes soaked swelling 4～6 hours, and suction filtration is clean, replaced micro-dimethoxym ethane down with methyl alcohol at last, and the deionized water backwash is to not having the methyl alcohol flavor and using ultraviolet specrophotometer OD
210nm=0.;
After C, additive-crosslinking reaction finish, reactor be cooled off with cold water rapidly, and product water is washed till room temperature,
Filter; Product soaked 2～8 hours with acetone with acetone drip washing two times again, carried out back flow reaction 4～6 hours in the acetone soln of 0.5～2moL/LHCL, filtered, drained; Add and to contain the methanol solution that alkali concn is 0.5～2moL/L, carried out back flow reaction 4～6 hours, filter, drain, use absolute ethyl alcohol drip washing, at last with alcohol extract to ultraviolet specrophotometer OD
254nm＜0.03.
5, the preparation method of sorbing material as claimed in claim 4 is characterized in that also comprising the material surface chemical modification reaction:
Polymeric adsorbent behind the purifying is dropped in the reactor, carry out the polymeric adsorbent surface chemical modification with 0.2～1.2% collodion ethanolic solution; Then, filtration drying.
6, the preparation method of sorbing material as claimed in claim 5 is characterized in that the collodion modified membrane thickness of resin surface is 3～5 microns.
7, a kind of use makes the high crosslinked macroporous absorbent resin of the equal hole pattern shape of medical grade as the preparation method of claim 1 or 2 or 3 described sorbing materials, it is characterized in that
Physical features is:
1) outward appearance: light yellow or golden yellow opaque spherical particle,
2) particle diameter: 0.6～1.2mm,
3) specific area: 680～820m
2/ g,
4) average pore size: 8.0～20.0nm,
5) pore volume: 0.48～0.56ml/g,
6) porosity: 0.52～0.62%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610087443 CN101088599A (en) | 2006-06-12 | 2006-06-12 | Prepn and product of adsorbing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610087443 CN101088599A (en) | 2006-06-12 | 2006-06-12 | Prepn and product of adsorbing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101088599A true CN101088599A (en) | 2007-12-19 |
Family
ID=38942196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610087443 Pending CN101088599A (en) | 2006-06-12 | 2006-06-12 | Prepn and product of adsorbing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101088599A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104353143A (en) * | 2014-11-28 | 2015-02-18 | 于杰 | Adsorbent for treating drug dependence and usage thereof |
| CN104667896A (en) * | 2013-08-12 | 2015-06-03 | 天津市阳权医疗器械有限公司 | Styrene-series resin adsorbent new structural product for removing high triglyceride from blood |
| CN105085829A (en) * | 2015-08-17 | 2015-11-25 | 珠海健帆生物科技股份有限公司 | Preparation method of macroporous adsorbent resin for toxin substance adsorption |
| CN108623733A (en) * | 2017-03-24 | 2018-10-09 | 鹤壁市山城区牟山大道大唐离子交换树脂应用研究所 | Resin intermediate containing Third monomer |
| CN108793155A (en) * | 2018-07-03 | 2018-11-13 | 济南大学 | A kind of preparation method of high-specific surface area lotus root shape porous carbon materials |
| CN109833854A (en) * | 2019-03-04 | 2019-06-04 | 蚌埠市天星树脂有限责任公司 | A kind of macroporous absorbent resin and preparation method thereof |
| CN111389377A (en) * | 2020-03-25 | 2020-07-10 | 旬阳领盛新材料科技有限公司 | Method for producing post-crosslinked adsorption resin by one-pot method |
-
2006
- 2006-06-12 CN CN 200610087443 patent/CN101088599A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667896A (en) * | 2013-08-12 | 2015-06-03 | 天津市阳权医疗器械有限公司 | Styrene-series resin adsorbent new structural product for removing high triglyceride from blood |
| CN104667896B (en) * | 2013-08-12 | 2016-12-28 | 天津市阳权医疗器械有限公司 | For removing the phenylethylene resin series adsorbent of high triglyceride in blood |
| CN104353143A (en) * | 2014-11-28 | 2015-02-18 | 于杰 | Adsorbent for treating drug dependence and usage thereof |
| CN105085829A (en) * | 2015-08-17 | 2015-11-25 | 珠海健帆生物科技股份有限公司 | Preparation method of macroporous adsorbent resin for toxin substance adsorption |
| CN105085829B (en) * | 2015-08-17 | 2017-08-29 | 珠海健帆生物科技股份有限公司 | The preparation method of the macroporous absorbent resin adsorbed for toxic substance |
| CN108623733A (en) * | 2017-03-24 | 2018-10-09 | 鹤壁市山城区牟山大道大唐离子交换树脂应用研究所 | Resin intermediate containing Third monomer |
| CN108793155A (en) * | 2018-07-03 | 2018-11-13 | 济南大学 | A kind of preparation method of high-specific surface area lotus root shape porous carbon materials |
| CN109833854A (en) * | 2019-03-04 | 2019-06-04 | 蚌埠市天星树脂有限责任公司 | A kind of macroporous absorbent resin and preparation method thereof |
| CN111389377A (en) * | 2020-03-25 | 2020-07-10 | 旬阳领盛新材料科技有限公司 | Method for producing post-crosslinked adsorption resin by one-pot method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101088598A (en) | Prepn and product of adsorbing material | |
| CN101088600A (en) | Prepn and product of adsorbing material | |
| CN101088599A (en) | Prepn and product of adsorbing material | |
| CN101088603A (en) | Prepn and product of adsorbing material | |
| CN104927063B (en) | A kind of method of adsorption recovery Phenols In Industrial Liquid Waste class compound and the preparation method of sorbing material | |
| US20110288191A1 (en) | Macroporous absorbent resin for extracting cephalosporin c and method of preparation | |
| CN105418946A (en) | Preparation method of secondarily-crosslinked adsorption resin | |
| CN102049242A (en) | Anion resin for bilirubin absorption and preparation method thereof | |
| CN108276526A (en) | A kind of high carrying capacity large aperture polymer cation displacement chromatography medium and its preparation | |
| JPS59182802A (en) | High molecular weight carbonyl group-containing substance useful as absorbent for nitrogen compound | |
| CN110117379B (en) | Adsorbing material for removing LDL (low density lipoprotein) in blood perfusion and preparation method thereof | |
| CN108939940A (en) | A kind of modification PVDF flat-plate separation film with anticoagulation function | |
| CN105820282B (en) | A kind of high stability hydrogen bonds are to receptor macroporous absorbent resin and its synthetic method | |
| CN101088601A (en) | Prepn and product of adsorbing material | |
| CN104530274B (en) | Method for adsorbing and separating gulonic acid by using ultrahigh cross-linked resin | |
| CN103328201A (en) | Compositions and methods useful in selectively modifying the internal and external surfaces of porous polymer beads | |
| CN101864038A (en) | Surface grafting polar monomer modified polystyrene macroporous resin and preparation method thereof | |
| CN101088602A (en) | Prepn and product of adsorbing material | |
| CN109180850A (en) | A kind of composite pore-forming is preparing the application in macroreticular ion exchange resin | |
| EP0060472B1 (en) | A method for separating t cells from leukocytes | |
| CN101381426A (en) | Linking dithizone resin and preparation method thereof | |
| JP2002102719A (en) | Mixed bed type ion exchange resin bed and anion exchange resin used in the same | |
| CN103316643A (en) | Modified adsorption resin and preparation method thereof | |
| CN115975321A (en) | Hydrogel, filter material for removing white blood cells in pet blood and preparation method thereof | |
| SU497781A3 (en) | The method of obtaining sulfonated macrorelate porous copolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |