CN102423687A - Preparation method of resin carbon for blood purification - Google Patents
Preparation method of resin carbon for blood purification Download PDFInfo
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- CN102423687A CN102423687A CN2011102256184A CN201110225618A CN102423687A CN 102423687 A CN102423687 A CN 102423687A CN 2011102256184 A CN2011102256184 A CN 2011102256184A CN 201110225618 A CN201110225618 A CN 201110225618A CN 102423687 A CN102423687 A CN 102423687A
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Abstract
The invention discloses a method for preparing resin cable which can effectively adsorb medium molecular substances. The method comprises the following step of directly utilizing porous polystyrene-divinylbenzene microspheres with ultra-high crosslinking degree to perform carbonization so as to get the spherical resin carbon which is in the particle size of 300 mu m-1.5mm and in the specific surface area (BET: Brunauer-Emmett-Teller) of 500-2000m<2>/g. The method is simple in process flow and small in pollution and simultaneously has excellent adsorption performance and biocompatibility against the medium molecular substances in body fluid of a human body.
Description
Technical field
The invention belongs to the medical material field, specifically, relate to a kind of preparation and be used for the method that blood perfusion can effectively adsorb medium molecular substance resin charcoal.
Background technology
Renal failure in late period patient need earn a bare living by dialysis; Can remove the small-molecule substance in the blood effectively through dialysis membrane; But the modern medical service detection means clearly realizes that people more to be also had more middle molecular substance (0.5 ~ 60kDa) is the key substance that influences patient health, and these materials are difficult to effective removal by dialysis.One Chinese patent application 200410064533.2 has proposed a kind of method for preparation of active carbon that effectively medium molecular substance is adsorbed; But it utilizes the polystyrene of secondary cross-linking to carry out charing for the basis; Need use like this like internationally recognized carcinogens such as chloromethyl ethers as crosslinking agent, technology is comparatively complicated.Simultaneously, selling thermosetting polyphenylene vinyl microballoon major part on the market all is to carry out secondary cross-linking with this route.Because the polymer microballoon internal-response is active different; Will cause when secondary cross-linking; The pore-size distribution inequality that resin is inner; Poor with regard to inner aperture monodispersity after directly causing resin to carry out charing like this, its influence is that the absorption property of target substance is reduced and the absorption of normal protein is increased, and reduces its biocompatibility.
The resin charcoal is a kind of as active carbon, because its purity is high, mechanical strength is good, and specific area is big, is widely used in biomedicine field.Keep renal failure patient life aspect, no matter haemodialysis or blood perfusion, can effectively remove medium molecular substance has become and has weighed whether effectively criterion of methods of treatment.Resin charcoal behind the coating as an effective wide spectrum adsorbent from last century the seventies just use with clinical.Because preparation technology and raw-material relation, cause the inner pore-size distribution of resin charcoal wider, and the resin charcoal that possesses more macropore adsorb large molecular weight protein material such as albumin and blood platelet more easily when blood perfusion.Ramsden reported once that the more albumin of absorption can reduce the removing of adsorbent to noxious material in the uremic patient blood greatly.Therefore aspect medium molecular substance absorption, not only need high-specific surface area, simultaneously pore size and distribution thereof are all had higher requirement.
The polystyrene-based microballoon of superhigh cross-linking degree is widely used in separating adsorbing domain always, and it is simple to it is characterized in that possessing the preparation method, characteristics such as the easy control of internal holes gauge structure.But owing to the hydrophobicity of polystyrene itself is easy to adsorb a large amount of macromolecular substances such as albumen, and these materials are the indispensable benefit materials in the human body as albumin, therefore seldom it are directly used separately in the blood perfusion field.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide a kind of preparation good biocompatibility, the centering molecule has the method than the spherical resin charcoal of high absorption capacity.
The present invention seeks to realize like this:
Concrete preparation process of the present invention is following:
1, the preparation of superhigh cross-linking degree polystyrene-divinyl microballoon
Styrene and divinyl benzene monomer are pressed mass ratio 1:1 ~ 1:2 dispose oil phase; The initator benzoyl peroxide and the 0 ~ 40%wt pore-foaming agent that add styrene and divinyl benzol mixture 0.5 ~ 1%wt simultaneously; Adopt suspension polymerization; Polyvinyl alcohol with styrene and divinyl benzol mixture 3% ~ 10%wt is a stabilizing agent, oil phase is joined stirring reaction made superhigh cross-linking degree microballoon in 12 ~ 24 hours in 80 ℃ of water.Wherein, pore-foaming agent is a toluene, wherein a kind of of naphthalene, paraffin oil, octane, hexadecane, perhaps two kinds mixture wherein.The microballoon water or the acetone that prepare are clean.
2, pre-oxidation
Superhigh cross-linking degree polystyrene-divinylbenzene microspheres after separate cleaning is put into oxygen content at 10 ~ 40% atmosphere, in 3 hours, rise to 200 ℃, and kept 1 ~ 8 hour, obtain the resin charcoal of pre-oxidation by room temperature.
3, charing and activation
The resin carbon microspheres of pre-oxidation under nitrogen atmosphere, slowly is warmed up to 800 ℃ ~ 1100 ℃ and carried out carbonization reaction 60 minutes ~ 180 minutes, fed steam activation then 10 minutes ~ 120 minutes.
Through the spherical resin carbon granule footpath of above method preparation at 300 μ m ~ 1.5mm, specific area (BET) 500 ~ 2000m
2/ g, surface gloss is good, and intensity is high, possesses good middle Molecular Adsorption ability and good biocompatibility simultaneously.
In experiment in vitro, (14.4kDa) represents medium molecular substance with lysozyme.In the cushioning liquid of pH7.2, the lysozyme soln 200mL of configuration 100mg/L and the people's of 200mg/L albumin solution 100mL; Resin charcoal behind 1mL resin charcoal or the coating is put into these solution; Under 37 ℃, concussion absorption was measured the residual concentration of solute in the solution after 2 hours in the shaking table of 60rpm; Calculate the adsorption rate of adsorbent, the result sees table 1.
The absorption property of table 1 resin charcoal
Can find out that by last table the middle molecular substance lysozyme is had higher adsorption rate, but very low to the albuminous absorption in the blood of human body simultaneously.Very low to the absorption property decline of lysozyme through the resin charcoal behind the coating, albuminous absorption is decreased, so the raising of the resin charcoal behind coating biocompatibility, keep higher adsorption capacity simultaneously again to target substance.
Beneficial effect:
The present invention is a raw material with styrene and divinyl benzene monomer, and the polystyrene-divinylbenzene microspheres through suspension polymerization superhigh cross-linking degree is the charing raw material.Wherein, also can use a certain amount of pore-foaming agent to regulate the inner pore size of microballoon in the polymerization process, to prepare suitable charing raw material.The charing raw material through charing and activation, has been obtained specific area (BET) 500 ~ 2000m
2The spherical resin charcoal of/g.Production technology of the present invention is simple, pollution is little, yield is high, product purity is high, and raw material is prone to obtain simultaneously, can realize the large-scale production preparation.
The specific embodiment
Embodiment 1
Adding 1g benzoyl peroxide and 40g paraffin oil are made into oil-phase solution in the mixed solution of 100g styrene and 100g divinylbenzene, and it is subsequent use to stir.Simultaneously, the 18g polyvinyl alcohol is dissolved in the 2L deionized water, stirring is dissolved it fully.Having under the condition of stirring, the oil phase for preparing is slowly joined in the poly-vinyl alcohol solution, logical nitrogen is warmed up to 80 ℃ of reactions 18 hours after 1 hour.Water and acetone cleaned microballoon repeatedly after reaction finished.
To put into oxygen content be 20% atmosphere with cleaning microballoon after the screening, rises to 200 ℃ by room temperature in 3 hours, and kept 3 hours.Subsequently the microballoon of pre-oxidation is put in the nitrogen atmosphere, and be warmed up to 900 ℃, after this temperature keeps 2 hours, fed steam activation 1 hour, can obtain the spherical resin charcoal of the shiny black gloss of outward appearance with 1 ℃ of/minute speed.
Resin charcoal specific area (BET) 786m that detection prepares
2/ g.According to the method for previous description, behind the test gained resin charcoal coating lysozyme and albuminous adsorption rate are respectively 70.5% and 8.4%.
Embodiment 2
Adding 1g benzoyl peroxide and 30g naphthalene are made into oil-phase solution in the mixed solution of 60g styrene and 100g divinylbenzene, and it is subsequent use to stir.Simultaneously the 15g polyvinyl alcohol is dissolved in the deionized water of 1.6L, stirring is dissolved it fully.Having under the condition of stirring, the oil phase for preparing is slowly joined in the poly-vinyl alcohol solution, logical nitrogen is warmed up to 80 ℃ of reactions 24 hours after 1 hour.Water and acetone cleaned microballoon repeatedly after reaction finished.
To put into oxygen content be 30% atmosphere with cleaning microballoon after the screening, rises to 200 ℃ by room temperature in 3 hours, and kept 3 hours.Subsequently the microballoon of pre-oxidation is put in the nitrogen atmosphere, and be warmed up to 800 ℃, after this temperature keeps 3 hours, fed steam activation 1 hour, can obtain the spherical resin charcoal of the shiny black gloss of outward appearance with 1 ℃ of/minute speed.
Resin charcoal specific area (BET) 1035m that detection prepares
2/ g.According to the method for previous description, behind the test gained resin charcoal coating lysozyme and albuminous adsorption rate are respectively 72.7% and 6.9%.
Embodiment 3
In the mixed solution of 60g styrene and 100g divinylbenzene, add 1g benzoyl peroxide, 5g naphthalene and 15g toluene and be made into oil-phase solution, it is subsequent use to stir.Simultaneously the 15g polyvinyl alcohol is dissolved in the deionized water of 1.6L, stirring is dissolved it fully.Having under the condition of stirring, the oil phase for preparing is slowly joined in the poly-vinyl alcohol solution, logical nitrogen is warmed up to 80 ℃ of reactions 24 hours after 1 hour.Water and acetone cleaned microballoon repeatedly after reaction finished.
To put into oxygen content be 30% atmosphere with cleaning microballoon after the screening, rises to 200 ℃ by room temperature in 3 hours, and kept 3 hours.Subsequently the microballoon of pre-oxidation is put in the nitrogen atmosphere, and be warmed up to 900 ℃, after this temperature keeps 3 hours, fed steam activation 1 hour, can obtain the spherical resin charcoal of the shiny black gloss of outward appearance with 1 ℃ of/minute speed.
Resin charcoal specific area (BET) 1105m that detection prepares
2/ g.According to the method for previous description, behind the test gained resin charcoal coating lysozyme and albuminous adsorption rate are respectively 71.5% and 6.1%.
Embodiment 4
In the mixed solution of 100g styrene and 100g divinylbenzene, add the 2g benzoyl peroxide and be made into oil-phase solution, it is subsequent use to stir.Simultaneously, the 20g polyvinyl alcohol is dissolved in the 2L deionized water, stirring is dissolved it fully.Having under the condition of stirring, the oil phase for preparing is slowly joined in the poly-vinyl alcohol solution, logical nitrogen is warmed up to 80 ℃ of reactions 18 hours after 1 hour.Water and acetone cleaned microballoon repeatedly after reaction finished.
To put into oxygen content be 20% atmosphere with cleaning microballoon after the screening, rises to 200 ℃ by room temperature in 3 hours, and kept 3 hours.Subsequently the microballoon of pre-oxidation is put in the nitrogen atmosphere, and be warmed up to 900 ℃, after this temperature keeps 2 hours, fed steam activation 1 hour, can obtain the spherical resin charcoal of the shiny black gloss of outward appearance with 1 ℃ of/minute speed.
Resin charcoal specific area (BET) 1101m that detection prepares
2/ g.According to the method for previous description, behind the test gained resin charcoal coating lysozyme and albuminous adsorption rate are respectively 72.5% and 8.1%.
Embodiment 5
In the mixed solution of 100g styrene and 200g divinylbenzene, add 1.5g benzoyl peroxide and 90g toluene and 30g hexadecane and be made into oil-phase solution, it is subsequent use to stir.Simultaneously, the 9g polyvinyl alcohol is dissolved in the 2L deionized water, stirring is dissolved it fully.Having under the condition of stirring, the oil phase for preparing is slowly joined in the poly-vinyl alcohol solution, logical nitrogen is warmed up to 80 ℃ of reactions 18 hours after 1 hour.Water and acetone cleaned microballoon repeatedly after reaction finished.
To put into oxygen content be 20% atmosphere with cleaning microballoon after the screening, rises to 200 ℃ by room temperature in 3 hours, and kept 3 hours.Subsequently the microballoon of pre-oxidation is put in the nitrogen atmosphere, and be warmed up to 900 ℃, after this temperature keeps 2 hours, fed steam activation 1 hour, can obtain the spherical resin charcoal of the shiny black gloss of outward appearance with 1 ℃ of/minute speed.
Resin charcoal specific area (BET) 1213m that detection prepares
2/ g.According to the method for previous description, behind the test gained resin charcoal coating lysozyme and albuminous adsorption rate are respectively 71.5% and 7.1%.
Claims (5)
1. preparation method who is used for the resin charcoal of blood purification is characterized in that carrying out as follows:
1) be oil phase with styrene and divinyl benzene monomer mixed configuration; The benzoyl peroxide that adds styrene and divinyl benzol mixture 0.5 ~ 1%wt simultaneously; Adopt suspension polymerisation; Polyvinyl alcohol with styrene and divinyl benzol mixture 3% ~ 10%wt is a stabilizing agent, oil phase is joined stirring reaction made superhigh cross-linking degree microballoon in 12 ~ 24 hours in 80 ℃ of water;
2) will separate superhigh cross-linking degree polystyrene-divinylbenzene microspheres after cleaning and put into oxygen content, and in 3 hours, rise to 200 ℃, and kept 1 ~ 8 hour, obtain the resin charcoal of pre-oxidation by room temperature at 10 ~ 40% atmosphere;
3) with the resin carbon microspheres of pre-oxidation under inert gas environment, carried out carbonization reaction 60 minutes ~ 180 minutes in 800 ℃ ~ 1100 ℃, feed steam activation then and obtained the resin charcoal in 10 minutes ~ 120 minutes.
2. according to the said a kind of preparation method who is used for the resin charcoal of blood purification of claim 1, it is characterized in that: also add styrene and divinyl benzol mixture 40%wt when adding benzoyl peroxide in the said step (1) with interior pore-foaming agent.
3. according to the said a kind of preparation method who is used for the resin charcoal of blood purification of claim 1, it is characterized in that: inert gas is nitrogen or helium in the said step (3).
4. according to the said a kind of preparation method who is used for the resin charcoal of blood purification of claim 1, it is characterized in that: said styrene and the mixing of divinyl benzene monomer are configured to oil phase by mass ratio 1:1 ~ 2.
5. according to the said a kind of preparation method who is used for the resin charcoal of blood purification of claim 1, it is characterized in that: said pore-foaming agent is wherein a kind of of toluene, naphthalene, paraffin oil, octane and hexadecane or more than one mixture.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795624A (en) * | 2012-08-31 | 2012-11-28 | 天津大学 | Low-energy-consumption preparation method of pitch-based spherical active carbon |
| CN104525149A (en) * | 2014-11-10 | 2015-04-22 | 苏州维泰生物技术有限公司 | Middle molecule adsorbent for epidemic hemorrhagic fever and preparation method thereof |
| CN105032373A (en) * | 2015-05-29 | 2015-11-11 | 珠海健帆生物科技股份有限公司 | Adsorbent with bionic film coating material and preparation method thereof |
| CN105504131A (en) * | 2016-01-26 | 2016-04-20 | 重庆希尔康血液净化器材研发有限公司 | Preparing method for resin for clearing away beta2-microglobulin in blood purification |
| CN106268703A (en) * | 2015-11-04 | 2017-01-04 | 珠海健帆生物科技股份有限公司 | DNA immunization adsorbent and preparation method thereof |
| CN106744943A (en) * | 2016-12-10 | 2017-05-31 | 郑鑫 | A kind of preparation method of spherical polystyrene activated carbon |
| CN109513429A (en) * | 2017-09-18 | 2019-03-26 | 重庆希尔康血液净化器材研发有限公司 | A kind of preparation method of modified adsorbent for bilirubin |
| CN110496600A (en) * | 2019-08-26 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of preparation method and application of the core-shell structure magnetic material of porous carbon package cobalt |
| CN112808231A (en) * | 2020-12-09 | 2021-05-18 | 清华大学 | Porous spherical carbon adsorption material with blood compatibility and preparation method thereof |
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| CN101612543A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | Be used for the preparation of the polystyrene-divinylbenzene microspheres of blood purification |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795624A (en) * | 2012-08-31 | 2012-11-28 | 天津大学 | Low-energy-consumption preparation method of pitch-based spherical active carbon |
| CN104525149A (en) * | 2014-11-10 | 2015-04-22 | 苏州维泰生物技术有限公司 | Middle molecule adsorbent for epidemic hemorrhagic fever and preparation method thereof |
| CN104525149B (en) * | 2014-11-10 | 2016-11-02 | 浙江康诚工业产品设计有限公司 | Middle molecule adsorbent for epidemic hemorrhagic fever and preparation method thereof |
| CN105032373A (en) * | 2015-05-29 | 2015-11-11 | 珠海健帆生物科技股份有限公司 | Adsorbent with bionic film coating material and preparation method thereof |
| CN105032373B (en) * | 2015-05-29 | 2017-11-24 | 珠海健帆生物科技股份有限公司 | A kind of adsorbent with bionical coated fertilizer and preparation method thereof |
| CN106268703B (en) * | 2015-11-04 | 2018-11-30 | 珠海健帆生物科技股份有限公司 | DNA immunization adsorbent and preparation method thereof |
| CN106268703A (en) * | 2015-11-04 | 2017-01-04 | 珠海健帆生物科技股份有限公司 | DNA immunization adsorbent and preparation method thereof |
| CN105504131A (en) * | 2016-01-26 | 2016-04-20 | 重庆希尔康血液净化器材研发有限公司 | Preparing method for resin for clearing away beta2-microglobulin in blood purification |
| CN106744943A (en) * | 2016-12-10 | 2017-05-31 | 郑鑫 | A kind of preparation method of spherical polystyrene activated carbon |
| CN109513429A (en) * | 2017-09-18 | 2019-03-26 | 重庆希尔康血液净化器材研发有限公司 | A kind of preparation method of modified adsorbent for bilirubin |
| CN110496600A (en) * | 2019-08-26 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of preparation method and application of the core-shell structure magnetic material of porous carbon package cobalt |
| CN110496600B (en) * | 2019-08-26 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method and application of core-shell structure magnetic material with porous carbon coated with cobalt |
| CN112808231A (en) * | 2020-12-09 | 2021-05-18 | 清华大学 | Porous spherical carbon adsorption material with blood compatibility and preparation method thereof |
| CN112808231B (en) * | 2020-12-09 | 2022-04-08 | 清华大学 | Porous spherical carbon adsorption material with blood compatibility and preparation method thereof |
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Application publication date: 20120425 |