CN107011481A - A kind of preparation method of endotoxin absorbent - Google Patents

A kind of preparation method of endotoxin absorbent Download PDF

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Publication number
CN107011481A
CN107011481A CN201610057333.7A CN201610057333A CN107011481A CN 107011481 A CN107011481 A CN 107011481A CN 201610057333 A CN201610057333 A CN 201610057333A CN 107011481 A CN107011481 A CN 107011481A
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preparation
resin
reaction
epoxy resin
aqueous solution
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CN107011481B (en
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邹汉法
董靖
欧俊杰
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • External Artificial Organs (AREA)

Abstract

Present invention relates particularly to a kind of preparation method of endotoxin absorbent, wherein endotoxin absorbent includes being bonded the histidine ligand in carrier surface as the porous epoxy resin and chemical covalent of carrier.The present invention is to prepare porous epoxy resin of the particle diameter at 100 μm -500 μm using suspension polymerization, mixed again with anhydrous ethylenediamine with epoxy resin, heating stirring obtains amine resin, amine resin and glutaraldehyde hybrid reaction are then obtained formaldehyde-based resin, finally endotoxin absorbent is obtained with histidine ligand reaction.

Description

A kind of preparation method of endotoxin absorbent
Technical field
The invention belongs to field of polymer technology, and in particular to a kind of preparation method of endotoxin absorbent.
Background technology
Endotoxemia is due to that endotoxin on the outer cell membrane of Gram-negative bacteria is discharged into blood and caused , it may occur in which in a variety of lysises, such as large-area burns, serious hepatitis, hepatic sclerosis disease, Body's immunity is badly damaged, and shock, disseminated intravascular coagulation, multiple organ dysfunction can be caused A series of serious pathological changes such as exhaustion, ultimately result in organ necrosis, irreversible shock and death, face Effective treatment method is there is no on bed.How to accomplish in time, effectively to remove or destroy interior in patient's body Toxin, is the key issue for treating endotoxemia.Abroad in Recent Years have developed a variety of anti-endotoxins Molecular biosciences preparation, but complex manufacturing, medicine source due to antibody is few, cost is high, and price is very high It is expensive, and there is no one kind can be by III phase clinical trials so far.
To some great difficult and complicated illness, blood purification therapy has unique curative effect, is that clinical treatment is indispensable Important means, wherein blood perfusion therapy be by adsorbent directly adsorb remove blood in it is poisonous into Part or morbid substance, reach purification blood, alleviate and treat the purpose of disease.Domestic and international researcher has been opened The method treatment endotoxemia of beginning research and utilization blood purification, discovery has certain effect.Wherein use It is to remove a kind of endotoxic very promising method that endotoxin absorbent, which carries out blood purification therapy,.Endogenous toxic material Plain adsorbent is from specific absorption part, energy selective absorption endotoxin.The affinity ligand reported How adhesive rhzomorph B, histidine, polycation part, deoxycholic acid etc., part mainly by ionic bond and Hydrophobic effect is combined with endotoxin, reaches the endotoxic purpose of removal.
The content of the invention
It is an object of the invention to provide a kind of new endotoxin absorbent and preparation method thereof, the endotoxin is inhaled Attached dose uses the epoxy high score that Inorganic whisker thing prestox acrylate POSS is that crosslinking agent is prepared from Son is carrier, and the histidine that selection induced by endotoxin has higher recognition capability and adsorption capacity is inhaled as endotoxin Attached part, is removed available for endotoxic in biochemical product and blood.
The technology path of the present invention is to use suspension polymerization using GMA as monomer, eight Methacrylate POSS be crosslinking agent, prepared in the presence of pore-foaming agent particle diameter 100 μm- The porous resin polymer microsphere of 500 μ ms.Reacted with the epoxide group on anhydrous ethylenediamine and resin Introduce amino.Then the resin with aldehyde radical is obtained with glutaraldehyde with the resin reaction with amino.Finally The histidine aqueous solution and mixed with resin react obtaining endotoxin absorbent.
Specifically include following content：
(1) preparation of porous epoxy resin
The aqueous solution containing dispersant is prepared, by GMA, prestox acrylate POSS, initiator and pore-foaming agent miscella are added in the aqueous solution, and heating stirring obtains porous microsphere tree Fat.
(2) prepared by formaldehyde-based resin
Mixed first with anhydrous ethylenediamine with epoxy resin, heating stirring obtains amine resin, then amine Base resin is mixed with glutaraldehyde solution, prepares formaldehyde-based resin.
(3) preparation of endotoxin absorbent
Endotoxin absorbent is obtained with the histidine aqueous solution and formaldehyde-based resin reaction.
Initiator described in above-mentioned reaction is benzoyl peroxide, and initiator is relative to monomer (metering system Acid glycidyl ester) mass percent be 0.5-10%.
The pore-foaming agent can select toluene, ethylbenzene, n-hexane, normal heptane, normal octane, n-amyl alcohol, neighbour Between one or two or more kinds of pore-foaming agents in Phthalates different volumes than mixture, pore-foaming agent Mass percent relative to monomer is listed in 50-200%.
The dispersant is polyvinyl alcohol and gelatin, mass ratio row 1 between the two:1-6, dispersant and water Mass percent be classified as 0.4-8%.
Step (1) described heating stirring is generally in 150-400r.p.m., and reaction temperature is generally at 70-80 DEG C.
The reaction of step (2) anhydrous ethylenediamine and epoxy resin is carried out in a heated condition, both it Between the ratio between mass number be 1-5:1.
The temperature of described aminated reaction is 60-90 DEG C, and the reaction time is 2-20 hours, and aldehyde radicalization is anti- The temperature answered is 30-50 DEG C, and the reaction time is 2-20 hours.
The ratio between mass number of glutaraldehyde and epoxy resin is 1-5:1；
The mass concentration of step (3) histidine aqueous solution is 0.5-10%, histidine and formaldehyde-based resin matter It is 1-5 to measure the ratio between number:100, reaction temperature is 40 DEG C, and the reaction time is 2-20 hours.
Advantages of the present invention is：Using the histidine without endogenous toxicity as part, mild reaction conditions are utilized The reaction of aldehyde amine has synthesized endotoxin adsorption material.
Embodiment
Embodiment 1
(1) preparation of porous epoxy resin
The aqueous solution 1L that it is 10g/L containing polyvinyl alcohol to prepare and gelatin is 20g/L is as suspension polymerisation Method prepares the aqueous phase solution of epoxy resin reaction system.120mg benzoyl peroxides are dissolved in containing 12mL GMA, 2g prestox acrylate POSS and 18mL n-amyl alcohols mixing it is molten In liquid, the oiliness mixed solution is added in 60mL aqueous phase solutions, obtained water-oil phase layering Mixed system under 300r.p.m. mechanical agitation speed at room temperature to stir 1 hour, then by temperature 80 DEG C are increased to, polymerisation 20 hours, obtained product epoxy resin is washed with acetone and ethanol successively Three times standby after being dried in vacuo 12 hours at 60 DEG C.
(2) prepared by formaldehyde-based resin
100mL ethylenediamines are added in 10g epoxy resin, is reacted 5 hours at 80 DEG C, obtains amine Base resin, is then mixed with the 100mL glutaraldehyde water solution of mass concentration 50% again, in 40 DEG C of stirrings Reaction obtains formaldehyde-based resin in 10 hours.
(3) preparation of endotoxin absorbent
Mass concentration is that 1% histidine aqueous solution 100mL is mixed with 30g formaldehyde-based resins, at 40 DEG C Reaction 8 hours, obtained product with water and ethanol with washing three times after being dried in vacuo 12 at 60 DEG C successively It is standby after hour.
Prepared adsorbent is endotoxin removal rate in 12Eu/mL endotoxin solution to 1mL concentration For 89.6%.
Embodiment 2
(1) preparation of porous epoxy resin
The aqueous solution 1L that it is 8g/L containing polyvinyl alcohol to prepare and gelatin is 12g/L is as suspension polymerization Prepare the aqueous phase solution of epoxy resin reaction system.200mg benzoyl peroxides are dissolved in containing 10mL The mixed solution of GMA, 5g prestox acrylate POSS and 20mL n-hexanes In, the oiliness mixed solution is added in the 60mL aqueous solution, the mixing of obtained water-oil phase layering System to be stirred 1 hour under 300r.p.m. mechanical agitation speed, then raises temperature at room temperature To 80 DEG C, polymerisation 20 hours, obtained product epoxy resin is washed three times with acetone and ethanol successively It is standby after being dried in vacuo 12 hours at 60 DEG C.
(2) preparation of formaldehyde-based resin
100mL ethylenediamines are added in 10g epoxy resin, is reacted 5 hours at 80 DEG C, obtains amine Base resin, is then mixed with the 100mL glutaraldehyde water solution of mass concentration 50% again, in 45 DEG C of stirrings Reaction obtains formaldehyde-based resin in 10 hours.
(3) preparation of endotoxin absorbent
Mass concentration is that 1% histidine aqueous solution 100mL is mixed with 30g formaldehyde-based resins, anti-at 45 DEG C Answer 8 hours, obtained product is small after vacuum drying 12 at 60 DEG C with washing three times with water and ethanol successively Shi Houbei is used.
Prepared adsorbent is endotoxin removal rate in 12Eu/mL endotoxin solution to 1mL concentration For 93.4%.

Claims (7)

1. a kind of preparation method of endotoxin absorbent, it is characterised in that：Used in the endotoxin absorbent Carrier is polymer microsphere；
Suspension polymerization is used using GMA as monomer, prestox acrylate POSS For crosslinking agent, porous epoxy resin polymer microsphere is prepared in the presence of pore-foaming agent；Use anhydrous second Diamines introduces amino with the epoxide group reaction on resin；It is then anti-with glutaraldehyde and the resin with amino The resin with aldehyde radical should be obtained；Finally the histidine aqueous solution and the mixed with resin with aldehyde radical are carried out anti- Endotoxin absorbent should be obtained.
2. according to the preparation method described in claim 1, it is characterised in that：Using suspension polymerisation legal system Porous epoxy resin polymer microsphere of the standby particle diameter in 100 μm of -500 μ m.
3. according to the preparation method described in claim 1, it is characterised in that：
Detailed process is as follows：
(1) preparation of porous epoxy resin：
The aqueous solution containing dispersant is prepared, by GMA, prestox acrylate POSS, initiator and pore-foaming agent miscella are added in the aqueous solution, and heating stirring obtains porous microsphere tree Fat；
(2) prepared by formaldehyde-based resin：
Mixed first with ethylenediamine with epoxy resin, heating stirring obtains amine resin, then amido tree Fat is mixed with glutaraldehyde solution, prepares formaldehyde-based resin；
(3) preparation of endotoxin absorbent：
Endotoxin absorbent is obtained with the histidine aqueous solution and formaldehyde-based resin reaction.
4. according to the preparation method described in claim 3, it is characterised in that：
Initiator described in above-mentioned reaction is benzoyl peroxide, quality percentage of the initiator relative to monomer Number is 0.5-10%；
The pore-foaming agent can select toluene, ethylbenzene, n-hexane, normal heptane, normal octane, n-amyl alcohol, neighbour One or two or more kinds in Phthalates, pore-foaming agent is listed in relative to the mass percent of monomer 50-200%；
The dispersant is polyvinyl alcohol and gelatin, mass percent row 1 between the two:1-6, disperses The mass percent of agent and water is classified as 0.4-8%.
5. according to the preparation method described in claim 3, it is characterised in that：
Step (1) described heating stirring is generally in 150-400r.p.m., and reaction temperature generally exists 70-80℃。
6. according to the preparation method described in claim 3, it is characterised in that：
The reaction of step (2) ethylenediamine and epoxy resin is carried out in a heated condition, between the two The ratio between mass number be 1-5:1；
The temperature of described aminated reaction is 60-90 DEG C, and the reaction time is 2-20 hours, and aldehyde radicalization is anti- The temperature answered is 30-50 DEG C, when the reaction time is 2-20；
The ratio between mass number of glutaraldehyde and epoxy resin is 1-5:1.
7. according to the preparation method described in claim 3, it is characterised in that：
The mass concentration of step (3) histidine aqueous solution is 0.5-10%, histidine and formaldehyde-based resin matter It is 1-5 to measure the ratio between number:100, reaction temperature is 40 DEG C, and the reaction time is 2-20 hours.
CN201610057333.7A 2016-01-27 2016-01-27 A kind of preparation method of endotoxin absorbent Active CN107011481B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112755973A (en) * 2020-12-16 2021-05-07 重庆天外天生物技术有限公司 Composite adsorption material applied to blood purification field and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1194179A (en) * 1997-03-26 1998-09-30 中国科学院大连化学物理研究所 Chemical modification of microporous nylon film and preparation of affinity film with histidine ligand
WO2005026224A1 (en) * 2003-09-17 2005-03-24 Gambro Lundia Ab Separating material
US20120123002A1 (en) * 2009-07-03 2012-05-17 Asahi Kasei Medical Co., Ltd. Method for purification of antibody using porous membrane having amino group and alkyl group both bound to graft chain immobilized on porous substrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1194179A (en) * 1997-03-26 1998-09-30 中国科学院大连化学物理研究所 Chemical modification of microporous nylon film and preparation of affinity film with histidine ligand
WO2005026224A1 (en) * 2003-09-17 2005-03-24 Gambro Lundia Ab Separating material
US20120123002A1 (en) * 2009-07-03 2012-05-17 Asahi Kasei Medical Co., Ltd. Method for purification of antibody using porous membrane having amino group and alkyl group both bound to graft chain immobilized on porous substrate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
商振华等: ""去除内毒素的柱亲和介质与膜亲和介质的制备和特征"", 《分析化学》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112755973A (en) * 2020-12-16 2021-05-07 重庆天外天生物技术有限公司 Composite adsorption material applied to blood purification field and preparation method thereof
CN112755973B (en) * 2020-12-16 2023-03-10 重庆天外天生物技术有限公司 Composite adsorption material applied to blood purification field and preparation method thereof

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