CN103483487B - Novel structure product, preparation method and use of styrenic resin - Google Patents

Novel structure product, preparation method and use of styrenic resin Download PDF

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Publication number
CN103483487B
CN103483487B CN201310347458.XA CN201310347458A CN103483487B CN 103483487 B CN103483487 B CN 103483487B CN 201310347458 A CN201310347458 A CN 201310347458A CN 103483487 B CN103483487 B CN 103483487B
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resin
swelling agent
add
temperature
catalyzer
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CN103483487A (en
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于杰
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Weihai Weigaoyangquan Biological Co., Ltd.
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TIANJIN YANGQUAN MEDICAL DEVICES CO Ltd
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Priority to CN201510291617.8A priority Critical patent/CN104857015A/en
Priority to CN201510120605.9A priority patent/CN104689804B/en
Application filed by TIANJIN YANGQUAN MEDICAL DEVICES CO Ltd filed Critical TIANJIN YANGQUAN MEDICAL DEVICES CO Ltd
Priority to CN201510291604.0A priority patent/CN104923185B/en
Priority to CN201510120761.5A priority patent/CN104667897B/en
Priority to CN201310347458.XA priority patent/CN103483487B/en
Priority to CN201510291602.1A priority patent/CN104941607B/en
Priority to CN201510120428.4A priority patent/CN104689803B/en
Priority to CN201510156544.1A priority patent/CN104815628B/en
Priority to CN201510120484.8A priority patent/CN104667896B/en
Priority to CN201510291616.3A priority patent/CN104887700A/en
Priority to CN201510291618.2A priority patent/CN104922147A/en
Priority to CN201510291587.0A priority patent/CN104887699A/en
Publication of CN103483487A publication Critical patent/CN103483487A/en
Priority to PCT/CN2014/000203 priority patent/WO2015014091A1/en
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    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • A—HUMAN NECESSITIES
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    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12—Antivirals
    • A61P31/14—Antivirals for RNA viruses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12—Antivirals
    • A61P31/14—Antivirals for RNA viruses
    • A61P31/18—Antivirals for RNA viruses for HIV
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12—Antivirals
    • A61P31/20—Antivirals for DNA viruses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P37/00—Drugs for immunological or allergic disorders
    • A61P37/02—Immunomodulators
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    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P39/00—General protective or antinoxious agents
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P7/00—Drugs for disorders of the blood or the extracellular fluid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P9/00—Drugs for disorders of the cardiovascular system
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    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds

Abstract

The invention provides a technical scheme on a novel structure product, a preparation method and use of styrenic resin. By changing a material structure of the styrenic resin including styrene-divinyl benzene resin, and styrenic macroporous anion exchange resin and gel anion exchange resin, concretely, embedding a metal element X into a styrenic resin skeleton, the styrenic resin has a new function more suitable for being used as a blood purification adsorbent.

Description

The new texture product of phenylethylene resin series, preparation method and its usage
Technical field
The present invention relates to phenylethylene resin series, particularly comprise the modified product of styrene-divinylbenzene, styrenic anion exchange resin, the preparation method of this product and application thereof.
Background technology
Phenylethylene resin series in prior art, comprises styrene-divinylbenzene, and styrenic anion exchange resin etc., as sorbent material and ion-exchanger, are widely used.
Use metallic compound such as FeCl 3catalyzer as phenylethylene resin series post-crosslinking reaction has been routine techniques.But, all in prior art up to now functional modification or modification are carried out to phenylethylene resin series, all do not relate to and the constitute of the carbon chain backbone of resin or element are improved, after participating in post-crosslinking reaction, do not enter the report in resin structure about catalyzer yet.In the report of prior art, after post-crosslinking reaction, cleaning solvent is usually used thoroughly to be removed by post-crosslinking reaction catalyzer.
In medical resin sorbent material Application Areas, modern medicine is to " virulence factor " systematic achievement in research.And to adopt blood purification therapy to remove " virulence factor " from human peripheral blood be a kind of simple and effective approach.To remove for the purpose of " virulence factor ", development new texture adsorbent material is put on the agenda.
In life science, lack a kind of simple and effective live body Dynamic sampling technique means, with dynamic extraction active molecular species sample from living organisms blood.
Summary of the invention
The object of the invention is to propose the new texture product of phenylethylene resin series, the technical scheme of preparation method and its usage.By changing phenylethylene resin series, comprise: styrene-divinyl benzene resin, and the structure of matter of polystyrene macroporous type anionite-exchange resin and gel-type anion exchange resin, make it to have the New function being more suitable as blood-purifying adsorbing agent, can be used for intravital blood purification and Dynamic sampling from intravital blood.
The present invention includes three partial contents:
First: the new texture product of phenylethylene resin series, i.e. modified phenylethylene-divinylbenzene macroporous adsorbent resin, and preparation method thereof.
This new texture product embeds metallic element X in the carbochain of cancellated styrene-divinyl benzene resin skeleton, and its structural formula is C-X-C; Wherein C is carbon, and X element is the metallic element with positive divalence or positive trivalent.
One of embodiment:
The metallic element X embedded is ferric iron element or trivalent aluminium element, and its structural formula is C-Fe-C or C-Al-C; Wherein the 3rd price of iron Fe or aluminium Al is avtive spot Y; Strong and weak according to the activity of element, Y site is element F (fluorine) or Elements C l (chlorine) or element B r (bromine) or I (iodine) successively; There is OH) time, be OH; Or there is the functional group of contraposition valence state.
Embodiment two:
The metallic element X embedded is divalent zinc element; Or described metallic element X is cupric element.
Divalent zinc element or cupric element do not have Y site.
The preparation method of the new texture product of this phenylethylene resin series: the preparation method being the modified phenylethylene-divinylbenzene macroporous adsorbent resin embedding metallic element X in skeleton; Specifically, in styrene-divinylbenzene macroporous adsorbent resin post-crosslinking reaction process, adopt ethylene dichloride or liquid alcohols to make swelling agent, adopt metallic element X compound solution as catalyzer; Under fully swelling condition, the boiling point making resin be warming up to swelling agent of heating, then the boiling point adding that catalyst solution continues to be warming up to catalyst solution, then add NaOH; Solution heats up tens of degree suddenly, make fully swelling resin under the condition exceeding swelling solution and the tens of degree temperature of catalyzer boiling point and fierce boiling, catalyzer adds reaction, in reaction process, almost just make the particle of metallic element X in catalyzer be embedded in the carbochain of resin matrix instantaneously; The add-on of catalyzer is relevant with the amount embedding metallic element X in carbochain, not by the restriction of insertion reaction.
Embodiment three:
In styrene-divinylbenzene macroporous adsorbent resin post-crosslinking reaction process, adopt ethylene dichloride or liquid alcohol to do resin swelling agent, adopt metallic element X compound solution as catalyzer;
The first step: macroporous resin is put into swelling agent and soaks, makes it fully swelling; Resin and the ratio of swelling agent add-on be resin quality than swelling agent volume, i.e. Kg/L, its ratio is selected between 1:3 to 1:30; Soak time was selected between 12 hours to 120 hours;
Second step: the resin through fully soaking being filtered free swelling solution, adding in reactor, the newer swelling solution of resin volume adding 1/2 immersion, swelling solution boiling point is warming up to after stirring, adding catalyzer makes temperature remain on swelling agent boiling point, continues to stir, and keeps two hours;
3rd step: again add catalyzer and elevate the temperature, continues to stir; When temperature is increased to catalyzer boiling point, stop adding;
4th step: continue to stir, keep temperature simultaneously, about two hours time, then add sodium hydroxide (NaOH), temperature of charge raises suddenly, stops adding sodium hydroxide, add water cooling when temperature is elevated to and exceeds catalyzer boiling point 25-35 DEG C, and reactive material is released from reaction container bottom, continue cooling;
5th step: reacted resin is rinsed well.
In above-mentioned post-crosslinking reaction process, adopt liquor ferri trichloridi or aluminum trichloride solution as catalyzer; Described metallic element X is metallic elements of ferrum, or metallic element aluminium.Adopt in the resin matrix obtained by liquor ferri trichloridi catalyzer and embed ferro element, resin is red or garnet; When sodium hydroxide is excessive, resin also can be black.
In above-mentioned post-crosslinking reaction process, also can adopt cupric chloride or adopt liquor zinci chloridi as catalyzer.Copper and zinc element do not have Y site in resin matrix.
Embodiment four:
The preparation method of the new texture product of above-mentioned phenylethylene resin series can also be:
Its 3rd step: when catalyzer to the temperature again added containing trivalent metallic element is elevated to 100 DEG C ± 5 DEG C instantaneously, add edible iodized salt and/or sugar defervescence, add-on is 0.5 to 1.5 times of catalyzer;
4th step: continue to stir, two hours time, then add sodium hydroxide (NaOH), temperature of charge raises again suddenly, to stopping when 130 DEG C adding sodium hydroxide when raising to temperature, adding water cooling, and reactive material is released from reaction container bottom;
5th step: reacted resin is rinsed well.
The Y site that gold in resin prepared by this method belongs to element can be occupied by I (iodine), monose, monose loop chain and OH-root, and performance has stronger polarity and the affinity to water.
The new texture product of the phenylethylene resin series of the second part of the present invention is modified phenylethylene series anion exchange resin, comprises modified macroporous type anionite-exchange resin, and modified gel type anionite-exchange resin, and preparation method thereof.
The carbochain of cancellated styrenic anion exchange resin skeleton embeds metallic element X, and its structural formula is C-X-C; Wherein X element is the metallic element with positive divalence or positive trivalent.
Embodiment five:
The metallic element X embedded is ferric iron element, or trivalent aluminium element; Its structural formula is C-Fe-C, or C-AL-C; Wherein the 3rd price of iron Fe or aluminium Al is avtive spot Y; Strong and weak according to the ripple alive of element, Y site is element F (fluorine) or Elements C l (chlorine) or element B r (bromine) or element I (iodine) successively; When there is OH, also can be OH; Or there is the functional group of pairing valence state.
Embodiment six:
The metallic element X embedded is divalent zinc element; Or cupric element.Its structural formula is: C-Zn-C, or: C-Cu-C.Zinc and copper do not have Y site in skeleton.
The preparation method of the modified styrene macroporous type anionite-exchange resin of metallic element X is embedded in skeleton:
The method and the aforementioned method embedding metallic element x in styrene-divinyl benzene resin skeleton similar.Specifically, in resin post-crosslinking reaction process, adopt ethylene dichloride or liquid alcohols to make swelling agent, adopt metallic element X compound solution as catalyzer; Heat under fully swelling condition, raise the temperature to swelling agent boiling point, keep temperature, add catalyzer, then be warming up to the boiling point of catalyst solution, then add NaOH, make temperature rising 25-35 DEG C suddenly, when fully swelling resin being in exceed the tens of degree temperature of its solution boiling point and catalyst reaction, in reaction process, almost just the particle of metallic element X is made to be embedded in the carbochain of resin matrix instantaneously.
Embodiment seven:
The present embodiment and styrene-divinylbenzene method of modifying have a little difference part, are in macroporous type anionite-exchange resin post-crosslinking reaction process:
The first step: resin is put into swelling agent and soaks, makes it fully swelling; Resin and the ratio of swelling agent add-on be resin quality than swelling agent volume, i.e. Kg/L, its ratio is selected between 1:6 to 1:60; Soak time was selected between 8 hours to 120 hours;
Second step: the resin through fully soaking is filtered free swelling solution, add in reactor, add the new swelling solution of the resin volume of 1/2 immersion again, heat after stirring, elevate the temperature to swelling agent boiling point, add catalyzer, and remain on swelling agent boiling temperature continuation stirring, keep two hours;
3rd step: again add catalyst solution, elevates the temperature to during catalyzer boiling point, continues stir about two hours;
4th step: then add sodium hydroxide (NaOH), reactant heats up suddenly, stops adding sodium hydroxide, and immediately cools when temperature is elevated to and exceeds catalyzer boiling point 25-35 DEG C;
5th step: reacted resin is rinsed well.
Adopt iron trichloride solvent or aluminum trichloride solution as catalyzer in aforesaid method.Or adopt liquor zinci chloridi or Cupric Chloride Solution as catalyzer.
Embodiment eight:
In above-mentioned post-crosslinking reaction process, adopt ethylene dichloride or liquid alcohol to do resin swelling agent, adopt iron trichloride or aluminum chloride solvent as catalyzer;
Its 3rd step: again adding when catalyzer to temperature is elevated to swelling agent boiling point, continues to stir; Keep temperature and add edible iodized salt and/or sugar defervescence, add-on is 0.5 to 1.5 times of catalyzer;
4th step: continue to stir, two hours time, then add sodium hydroxide (NaOH), temperature of charge raises suddenly, stops adding sodium hydroxide, adds water cooling, and reactive material released from reaction container bottom when temperature raises about 30 degree;
5th step: rinsed well by reacted resin, adopts liquor ferri trichloridi to be red, garnet as the resin that catalyzer obtains; When sodium hydroxide is excessive, can be black.
The Y site that gold in resin prepared by this method belongs to element can be occupied by I (iodine), monose, monose loop chain and OH, and performance has stronger polarity and the affinity to water.
The preparation method of metallic element X is embedded: in polystyrene gel-type anion exchange resin post-crosslinking reaction process in polystyrene gel-type anion exchange resin skeleton, adopt ethylene dichloride or liquid alcohols as swelling agent, use in the form of a solution as the metallic element iron cpd of catalyzer or metallic element aluminum compound.
Embodiment nine:
The first step: swelling agent makes resin fully swelling at normal temperatures, resin is resin quality with the ratio of swelling agent add-on: swelling agent volume, i.e. the ratio of Kg/L, and its ratio is 1:6 to 1:60; Soak time is 8 hours to 120 hours;
Second step: add catalyzer when swelling agent is heated to boiling point, temperature is kept after four hours, to add sodium hydroxide (NaOH), make resin suddenly be warming up to 92 to 96 DEG C and produce fierce boiling, metallic element x reactant heat up and in fierce boiling process embedded resin skeleton carbochain in, add water immediately and be cooled to normal temperature.
Embodiment ten:
In aforesaid method second step, the catalyzer added accounts for swellable resins ratio 1/10 and fully mixing, heat to during swelling agent boiling point and stop heating, keep temperature four hours, add again and account for the NaOH that resin reaction object amasss 20%, when making resin be warming up to reactant fierceness boiling (92 to 96 DEG C), immediately add and account for resin reaction object and amass the edible iodized salt of 20% and/or account for the sugar that resin reaction object amasss 20%, rapid defervescence, cooling, and release from reactor.
The Y site that gold in resin prepared by this method belongs to element can be occupied by I (iodine), monose loop chain and OH, and performance has stronger polarity and the affinity to water.
11 of embodiment:
In above-mentioned post-crosslinking reaction process, also Cupric Chloride Solution can be adopted, or liquor zinci chloridi is as catalyzer.The metallic element X embedded is divalent zinc element; Or cupric element.Its structural formula is: C-Zn-C, or: C-Cu-C.Zinc and copper do not have Y site in resin matrix.
Need to propose, styrene series anion exchange resin, comprises macroporous type and gel type resin, and after employing the inventive method modification, its ion-exchange performance is tending towards disappearing, and polarization absorption property obtain significant lifting.Gel type resin creates hole in modifying process, and in reality detects, the specific surface area of modified gel type resin can reach 1900M unexpectedly 2/ gram.
Part III content of the present invention is the purposes of the new texture product of phenylethylene resin series:
The pore diameter range of the polystyrene new texture resin adopted is 0-200nm, and pore volume and specific surface area are not limit; The Y site of the trivalent metallic element embedded in its skeleton is by OH occupy-place and/or by the occupy-place of monose loop chain and/or by the functional group occupy-place with contraposition valence state; Its purposes is used as Medical Adsorbents, for blood perfusion device; Or be used as oral resin sorbent; Or be used as the absorption sampling agent to molecule living matter in intravital blood; By Peripheral Circulation system or gi system, adsorption removal virulence factor wherein, or live body Dynamic sampling is carried out to virulence factor and living matter.
Resin aperture is prepared when resin polymerization reacts, relevant with the pore-creating agent material adopted.The inventive method, when participating in insertion reaction with metal catalyst, has dilating effect to resin aperture.Such as aforementioned, there is not hole in gel shape resin anion(R.A), but creates hole originally in reaction process, also defines by process the space that specific surface area reaches 1900 square meters/every grammes per square metre.
According to the needs that clinical diagnosis proposes, the new texture product of medical phenylethylene resin series according to its pore diameter range, following differentiation can be done:
12 of embodiment:
The aperture 0-20nm of the polystyrene new texture resin adopted, the resin wherein containing 5-20nm aperture is not less than 60%.
13 of embodiment:
The aperture 0-40nm of the polystyrene new texture resin adopted, the resin wherein containing 20-40nm aperture is not less than 60%.
14 of embodiment:
The aperture 0-60nm of the polystyrene new texture resin adopted, the resin wherein containing 40-60nm aperture is not less than 60%.
15 of embodiment:
The aperture 0-80nm of the polystyrene new texture resin adopted, the resin wherein containing 60-80nm aperture is not less than 60%.
16 of embodiment:
The aperture 0-100nm of the polystyrene new texture resin adopted, the resin wherein containing 80-100nm aperture is not less than 60%.
17 of embodiment:
The aperture 0-140nm of the polystyrene new texture resin adopted, the resin wherein containing 100-140nm aperture is not less than 60%.
18 of embodiment:
The aperture 0-200nm of the polystyrene new texture resin adopted, the resin wherein containing 140-200nm aperture is not less than 60%.
19 of embodiment:
When making sorbent material for blood perfusion device and using, select according to the valence state attribute of virulence factor of absorption and particle diameter the resin that there is contraposition valence state functional group and be suitable for aperture, fill blood perfusion device; The mode of filling is that a kind of resin of pore diameter range loads a tank, and blood perfusion device is according to the material valence state attributive classification in in-built resin aperture and Y site;
Or arrange according to the direction along blood flow warp, the large resin filling in aperture is at upstream position; Be loaded in perfusion device according to the order layering that aperture is descending is mixed, and according to the material valence state delamination classification that the element or functional group that occupy Y point have.
20 of embodiment:
Use for doing oral adsorbent agent, the resin of the different valence state material function that has with Y site group and different pore size respectively or be mixed in proportion and be packaged in medicinal slow releasing capsule.
21 of embodiment:
When using as intravital blood Middle molecule state living matter sampling agent, the different valence state material function group had with Y site and the resin of different pore size are loaded in sampling unit respectively.The similar blood perfusion device of structure of this sampling unit, using method also roughly the same.After completing sampling, sampler is extractd from blood extracorporeal circulation system, will the living beings wash-out in sampler resin be adsorbed on by the method for cleaning.Because resin of the present invention is the living matter adopting physical adsorption principle separation and Extraction blood Middle molecule state, be adsorbed in resin voids of the present invention and resin surface living matter can in nutrient environment for a long time in keep its vital activity, for life science provides a kind of important technique means.
In such use embodiment of the present invention, the pore diameter range of resin is from " 0 ", and refer to that aperture is " 0 ", namely resin particle does not have hole.But in a perfusion device or sampler, the gap between resin particle also can be regarded as in " aperture ", then " aperture " even should cannot measure concrete data, it perhaps can be very large, the aperture that serious offense resin particle can have.
Also any restriction is not done to " pore volume " and " specific surface area " in such use embodiment.Because for macroporous adsorbent resin, the most important condition that restriction adsorbed material enters resin voids is aperture.After aperture is determined, pore volume and specific surface area are proportional with Adsorbent rate respectively.And adsorption rate and aperture, proportionlity between pore volume and specific surface area are more statistics contents, not there is disruptive technology invention meaning of the present invention.
In a word, the new texture product of phenylethylene resin series of the present invention is used in blood perfusion device He in sampler makes sorbent material, due to the existence of avtive spot Y point, and can with multiple virulence factor in its polar adsorption function absorption blood; And can be occupied by monose loop chain due to Y point, all kinds of surface have glycan molecule, glycoprotein molecule virulence factor can because of affinity docile wound on it; This polar adsorption and affinity are wound around, also can produce to clash into or paste to virocyte shell in any case and tear effect, make intracellular virulence factor, such as small molecular virokine, viral RNA etc., waterfall type sprays and enters peripheral blood in cell, is just received by the large, medium and small aperture of polymeric adsorbent of the present invention and resin surface.
The effect of the avtive spot Y point that resin material of the present invention has, also be that Y point can by corresponding modification, occupied by the molecular function group with required function, thus for the polymeric adsorbent of all kinds of virulence factor is adsorbed in preparation targetedly, provide technology platform.
Arthus Claude Bernard proposes the theory about biotic environment balance; " in the external environment that biological existence is accustomed at it, and various in organism organize move in biological ˋ environment ' inner.The stable prerequisite being life and existing of environment; Environment is wanted often to keep balance with external environment, otherwise biological phenomena will get muddled." resin of the present invention set up with " competitive adsorption " rule biotic environment balance order in play a role.
The feature structure of resin of the present invention comprises: the salience(-cy) of Y point on skeleton, and the particle level film formed by the monose loop chain occupying Y point, and is wrapped in the Mierocrystalline cellulose coating on resin balls surface.The membrane permeation pressure utilizing resin balls surface and resin structure space to produce, effectively can pull out intracellular viral small molecules outside cytolemma when not destroying cell, and be adsorbed onto easily in resin.After hemoperfusion treatment terminates, the small molecules in cell and in peripheral blood, Middle molecule, macromole virus all can be adsorbed by perfusion device, indwelling, and takes out of in body; And reach and purify the blood, solve the disease that blood environment causes because of imbalance.
Based on the above material property that the present invention has, all kinds of medical polymeric adsorbent can be prepared pointedly, be applicable to following all kinds of illness:
1, acquired immune deficiency syndrome (AIDS), i.e. acquired immune deficiency syndrome (AIDS); Human immunodeficiency virus is RNA viruses, comprising: human immunodeficiency virus type 1 (HIV-1) and human immunodeficiency virus 2 type (HIV-2).
1.1, the rounded particle of electric Microscopic observation HIV-1, diameter is about 110nm; Adventitia has outer membrane glycoprotein (Env).
HIV-1 viral genome is about 10kb, and respectively there is a RNA sequence being called long terminal repetition (1ong terminal repeat, LTR) at two ends, are about 634bp.
New texture resin sorbent of the present invention is in HIV-1 virus replication regrouping process, to the virokine in each stage, all there is good adsorption, can blocks protein virus pass on, the a large amount of progeny virus produced in adsorption removal peripheral blood, stop virus fast-developing, and then remaining virokine is run its course in its life cycle.
1.2, the ultrastructure of HIV-2 and cell tropism similar to HIV-1.Resin sorbent of the present invention can infect virus by adsorption removal HIV-2 equally, blocks the inflammatory factor outburst of waterfall type.
2, resin sorbent of the present invention is to the virion of viral liver disease and Non-viral liver disease, has adsorption.
2.1, hepatitis A virus: be a kind of RNA viruses, belonging to pico+ribonucleic acid+virus section, is the spheroidal particle that diameter is about 27nm, forms symmetrical 20 body nucleocapsids, include line style single-stranded RNA by 32 shell particulates.This viral material is in the adsorption scope of resin of the present invention.
2.2, hepatitis B virus: be a kind of DNA virus, belonging to Hepadnaviridae (hepadnavividae), is the spheroidal particle of diameter 42nm.
2.3, serum of hepatitis B Patients can be looked into and see three kinds of particles under microscopical observation:
2.3.1, the pellet shapes particle of diameter 22nm;
2.3.2, tubular particle, be about 100 ~ 700nm, wide about 22nm;
2.3.3, diameter is the large spheroidal particle of 42nm, pellet shapes particle.
Pellet shapes particle and tubular particle are superfluous virus coat, containing surface antigen; Large spheroidal particle and virion, have solid and hollow two kinds, and hollow bead lacks nucleic acid.Three kinds of particles are all in the adsorbing scope of application of sorbent material of the present invention:
2,4, resin of the present invention has absorption Accommodation to antigen-antibody:
The form of hepatitis B surface antigen and surface antibody:
2.4.1, hepatitis B surface antigen(HBsAg) (HBsAg) and surface antibody (anti--HBs) HBsAg is present in the shell of virion and pellet shapes particle and tubular particle.
2.4.2, hepatitis BcAg (HBcAg) and core antibody (anti-HBc)
2.4.3, hepatitis B e antigen (HBeAg) and e antibody-(HBe).
Three kinds of antigen-antibodies are all in resin absorption sphere of action of the present invention.
2.5, resin of the present invention has affinity and specific adsorption effect to hepatitis C virus (HCV):
Hepatitis C virus (HCV) is a kind of RNA viruses with lipidic shell, diameter 50-60nm, and its genome is 10kb single strand RNA molecule.
2.6, resin of the present invention has affinity and specific adsorption effect to hepatitis D virus (HDV):
Hepatitis D virus (HDV) be a kind of defect addicted to liver single strand RNA virus, need the auxiliary of HBV just can copy, therefore the existing HBV of HDV is simultaneously or superinfection.HDV is the little garden spherical particle of diameter 35-37nm, and its shell is HBsAg, and inside is made up of the RNA molecule of a HDAg and 1.7kb.
2.7, resin of the present invention has affinity and specific adsorption effect to hepatitis E virus (HEV):
The picornavirus that hepatitis E virus (HEV) is diameter 27-34nm.
2.8, resin of the present invention has affinity and specific adsorption effect to hepatitis G virus (HGV):
3, resin of the present invention has adsorption to the inflammatory factor causing blood pressure to increase in patient body.
Vascular hypertension is divided into: a primary, b Secondary cases, and the vascular hypertension that the pathogenic factors such as c is viral are different is all relevant to the effect of excessive inflammatory factor.The inflammatory factor of vascular hypertension is small molecular, belongs to the scope of application of resin absorption effect of the present invention.
4, hyperinsulinemia is by the sufferer of the excessive initiation of Regular Insulin.
Resin of the present invention has obvious polar adsorption to insulin molecule excessive in patient body, Regular Insulin storage in control agent, may be used for treating hyperinsulinemia.
5, the autoimmune disorder etc. such as pernicious swollen, systemic lupus erythematous, the hemolytic anemia such as uremia, hepatopathy, Hematopoietic Malignancies, primary hepatocarcinoma, lung cancer, myelomatosis, all show increasing of serum beta-2-microglobulin content to reduce with glomerular filtration rate(GFR (GFR), synthesizing acceleration with B2M has substantial connection.Due to β 2the Middle molecular toxins accumulations such as microglobulin cause the incidence of dialysis related amyloidosis, renal osteodystrophy, Secondary Hyperparathyroidism etc. to increase, and cause all kinds of complication of patient thus, admission rate, mortality ratio also increase thereupon.
Resin of the present invention has the effect of adsorbing excessive B2-microglobulin, the excessive synthesis of β 2-microballoon egg in body can be blocked, remove the excessive Middle molecule toxicant being representative with B2-microglobulin, the biotic environment of the Diseases such as uremia, hepatopathy, lupus erythematosus, malignant tumour can be improved, improve Quality of Life of Patients.
6, drug dependence patient body internal cause is taken drugs and produces toxicity neuropeptide, blocks normal nerve signals conduction function.
Toxicity neuropeptide molecule in resin human peripheral blood of the present invention has adsorption, patient can being made in several tens minutes to cross over the withdrawal symptom phase fast, breaking away from the drug dependence to causing addiction medicine.
7, acute drugs poisoning is rescued.
Resin of the present invention, to the adsorption of toxicity neuropeptide material, can be applied to equally in the rescue to acute drugs poisoning patient, and have clinical verification case.
8, mental patient is given treatment to.
Resin of the present invention, to the adsorption of neuropeptide material, also can be used in giving treatment to mental patient, and has had clinical verification case.
9, hypertriglyceridemia (hypertriglyceridemia, HTG) is the synthesis of a kind of different race's property triglyceride level albumen or degraded obstacle.HTG refers to that the triglyceride level in blood is excessive with content in chylomicron and prebeta-lipoprotein, it and be atheroscleroticly formed with very large relation.Be called as " reticent killer "
Resin of the present invention can excessive chylomicron in the blood of adsorption removal hypertriglyceridemia (HTG) patient and beta lipoprotein, alleviates and even cures HTG sufferer.
10, hypercholesterolemia refers to that in the blood of patient, plasma cholesterol concentration is too high.1/3 of total plasma cholesterol exists in a free form, and 2/3 is the cholesteryl ester be combined with lipid acid.Plasma cholesterol is primarily of liver and small intestine synthesis.China is healthy between twenty and fifty many in 1400 ~ 1600 mg/litre, and the elderly is no more than 2000 mg/litre, more American-European artificially low.As treated more than 2500 mg/litre.
Resin sorbent of the present invention has adsorption to plasma cholesterol, and plasma cholesterol that can be excessive in adsorption removal body, alleviates and even cure hypercholesterolemia.
11, the adsorption of resin of the present invention is in the physical environment balance order set up with " competitive adsorption " rule, all kinds of lipoprotein that can exist in human peripheral blood, the plasma concentration comprising high and low density lipoprotein etc. carries out appropriate regulation, thus alleviates and cure hyperlipoproteinemia.
12, resin of the present invention has good equilibrium adsorption effect to lipid material excessive in Metabolic Syndrome Patients body.At use resin of the present invention as in the clinical trial of blood-purifying adsorbing agent, the triglyceride level average rate of decrease of patient is not less than 50%, the Regular Insulin average rate of decrease of hyperinsulinemia is not less than 60%, the rate of descent of LDL is not less than 35%, the average rate of decrease of VLDL is not less than 55%, the rate of descent of total cholesterol is not less than 35%.30% is not less than to the rate of descent of the Angiotensin of hypertension Metabolic syndrome patient, adjustable metabolic syndrome patient blood pressure.
13, resin of the present invention can effectively remove excessive in patient body in, macromole poisonous substance, to Middle molecule and in macromolecular viral H-N in clinical verification, obtain good effect, to rescuing the sudden pandemic (H1N1 caused by virus, H7N9, SARS) be very effective methods for the treatment of, and emergency measures.There is the case of clinical case.
14, resin of the present invention is to the interleukin-11 in Uveitis Patients blood, 6,18, has adsorption, can alleviate and even cure uveitis illness.
15, resin of the present invention to comprise high endotoxemia, pyemia crush syndrome blood samples of patients in small molecules, Middle molecule and macromole virulence factor have and well remove and adsorption.Effectively can rescue, alleviate and cure crush syndrome patient, patients with sepsis.
16, resin of the present invention can to the excessive inflammatory factor in blood; Interleukin, tumour necrosis factor, parathyroid hormone, endothelin, feritin, Angiotensin, hyperinsulinism etc. have adsorption removal effect targetedly.
17, resin of the present invention is to DIABLO through system balancing, hinders the newborn virulence factor of neural normal conduction effect to have adsorption, sexual hypofunction and impotence is had to the effect alleviated and cure in the process of Clinical practice, and its mechanism still requires study summary.
18, with resin of the present invention, blood purification treatment is done, the facial reddish brown in its postpartum and abdominal spot patterns to fertility puerpera, black can be alleviated fast; Present smooth belly and pale skin.
19, resin of the present invention can adsorb the virulence factor of various venereal disease, comprises bacterium and virus; For gonorrhoea in the process of clinical verification, pointed condyloma, the venereal diseases such as syphilis have the effect alleviated and cure.
20, resin of the present invention is used for the agent of living matter living body sampling, and its using method is identical with the using method as blood-purifying adsorbing agent in blood perfusion device, for life science provides a kind of simple and effective sampling technique means.
Preparation method's technical scheme that rosin products new texture technical scheme of the present invention and the present invention propose, all never sees the report of any open source literature before this, is unprecedented technical innovation in this area, compared with prior art has outstanding substantive distinguishing features.
The new texture product of phenylethylene resin series of the present invention uses as sorbent material in blood perfusion device, and adsorption effect is more excellent than the resin sorbent of prior art, and the scope of application is more extensive, is verified in test.The present invention has significant progress than prior art resin sorbent.
Adopt the blood perfusion device of material of the present invention and oral adsorbent agent to list the supporting technology of National 863 main project in, be incorporated into state science think tank a few days ago.

Claims (19)

1. phenylethylene resin series, is characterized in that: be modified phenylethylene-divinylbenzene macroporous adsorbent resin, the carbochain of cancellated styrene-divinyl benzene resin skeleton embeds metallic element X, its structural formula is C-X-C; Wherein C is carbon, and X element is the metallic element with positive divalence or positive trivalent; When described X element is trivalent metallic element, be ferric iron element or trivalent aluminium element, its structural formula is C-Fe-C or C-Al-C; Wherein the 3rd price of iron Fe or aluminium Al is avtive spot Y; Strong and weak according to the activity of element, Y site is element F (fluorine) or Elements C l (chlorine) or element B r (bromine) or I (iodine) successively; When there is OH, be OH; Or there is the functional group of contraposition valence state; When described metallic element X is divalent metal element, it is divalent zinc element; Or cupric element.
2. the preparation method of phenylethylene resin series as claimed in claim 1, is characterized in that: the preparation method being the modified phenylethylene-divinylbenzene macroporous adsorbent resin embedding metallic element X in skeleton; Specifically, in styrene-divinylbenzene macroporous adsorbent resin post-crosslinking reaction process, adopt ethylene dichloride or liquid alcohols to make swelling agent, adopt metallic element X compound solution as catalyzer; Under fully swelling condition, to heat the boiling point making resin be warming up to swelling agent, add the boiling point that catalyst solution continues to be warming up to catalyst solution again, adding sodium hydroxide again makes solution suddenly heat up tens of degree, under making the fully swelling resin condition that fierceness is seethed with excitement exceeding its boiling point tens of degree temperature, catalyst solution adds reaction, makes the particle of metallic element X in catalyst solution be embedded in the carbochain of resin matrix in the moment of reaction process; The add-on of catalyst solution is relevant with the amount embedding metallic element X in carbochain, not by the restriction of insertion reaction.
3. the preparation method of phenylethylene resin series as claimed in claim 2, it is characterized in that: in styrene-divinylbenzene macroporous adsorbent resin post-crosslinking reaction process, adopt ethylene dichloride or liquid alcohols to make swelling agent, adopt metallic element X compound solution as catalyzer; The first step: macroporous resin is put into swelling agent and soaks, makes it fully swelling; Resin and the ratio of swelling agent add-on be resin quality than swelling agent volume, i.e. Kg/L, its ratio is selected between 1:3 to 1:30; Soak time was selected between 12 hours to 120 hours; Second step: the resin through fully soaking being filtered free swelling agent, adding in reactor, the newer swelling agent of resin volume adding 1/2 immersion, swelling agent boiling point is warming up to after stirring, adding catalyst solution makes temperature remain on swelling agent boiling point, continues to stir, and keeps two hours; 3rd step: again add catalyst solution and elevate the temperature, continues to stir; When temperature is increased to catalyst solution boiling point, stop adding; 4th step: continue to stir, keep temperature simultaneously, two hours time, then add sodium hydroxide, temperature of charge raises suddenly, stops adding sodium hydroxide, add water cooling when temperature is elevated to and exceeds catalyst solution boiling point 25-35 DEG C, and reactive material is released from reaction container bottom, continue cooling; 5th step: reacted resin is rinsed well.
4. the preparation method of the phenylethylene resin series as described in claim 2 or 3, is characterized in that: in post-crosslinking reaction process, adopts liquor ferri trichloridi or aluminum trichloride solution as catalyzer; Liquor ferri trichloridi catalyzer gained resin is adopted to be red or garnet; When sodium hydroxide is excessive, resin can be black.
5. the preparation method of the phenylethylene resin series as described in claim 2 or 3, is characterized in that; In post-crosslinking reaction process, adopt Cupric Chloride Solution or adopt liquor zinci chloridi as catalyzer.
6. the preparation method of phenylethylene resin series as claimed in claim 3, it is characterized in that: its 3rd step: again adding when catalyst solution to temperature is elevated to 100 DEG C ± 5 DEG C instantaneously, add edible iodized salt and/or sugar defervescence, add-on is 0.5 to 1.5 times of catalyst solution; 4th step: continue to stir, two hours time, then add sodium hydroxide, temperature of charge raises again suddenly, stops adding sodium hydroxide, adds water cooling, and reactive material released from reaction container bottom when temperature is elevated to 130 DEG C; 5th step: reacted resin is rinsed well.
7. phenylethylene resin series, is characterized in that: be modified phenylethylene series anion exchange resin, comprises modified macroporous type anionite-exchange resin, and modified gel type anionite-exchange resin; The carbochain of cancellated styrene resin skeleton embeds metallic element X, and its structural formula is: C-X-C, and wherein C is carbon, and X element is the metallic element with positive divalence or positive trivalent; When described X element is trivalent metallic element, be ferric iron element or trivalent aluminium element, its structural formula is C-Fe-C or C-Al-C; Wherein the 3rd price of iron Fe or aluminium Al is avtive spot Y; Strong and weak according to the activity of element, Y site is element F (fluorine) or Elements C l (chlorine) or element B r (bromine) or I (iodine) successively; When there is OH, be OH; Or there is the functional group of contraposition valence state; When described metallic element X is divalent metal element, be divalent zinc element, its structural formula is C-Zn-C; Or cupric element, its structural formula is C-Cu-C.
8. the preparation method of phenylethylene resin series as claimed in claim 7, it is characterized in that: the preparation method being the modified styrene macroporous type anionite-exchange resin embedding metallic element X in skeleton: specifically, in resin post-crosslinking reaction process, adopt ethylene dichloride or liquid alcohols to make swelling agent, adopt metallic element X compound solution as catalyzer; Heat under fully swelling condition, raise the temperature to swelling agent boiling point, keep temperature, add catalyst solution, then be warming up to the boiling point of catalyst solution, then add sodium hydroxide, make temperature rising 25-35 DEG C suddenly, when fully swelling resin being in exceed its boiling point 25-35 DEG C and catalyst solution react, in reaction process, make the particle of metallic element be embedded in the carbochain of resin matrix instantaneously.
9. the preparation method of phenylethylene resin series as claimed in claim 8, is characterized in that: in macroporous type anionite-exchange resin post-crosslinking reaction process: the first step: resin is put into swelling agent and soaks, make it fully swelling; Resin and the ratio of swelling agent add-on be resin quality than swelling agent volume, i.e. Kg/L, its ratio is selected between 1:6 to 1:60; Soak time was selected between 8 hours to 120 hours; Second step: the resin through fully soaking is filtered free swelling agent and adds in reactor, add the new swelling agent of the resin volume of 1/2 immersion again, heat after stirring, elevate the temperature to swelling agent boiling point, add catalyst solution, and continue to stir in swelling agent boiling temperature, keep two hours; 3rd step: again add catalyst solution, elevates the temperature to during catalyzer boiling point, continues stirring two hours; 4th step: then add sodium hydroxide, reactant heats up suddenly, stops adding sodium hydroxide, and immediately cools when temperature is elevated to and exceeds catalyzer boiling point 25-35 DEG C; 5th step: reacted resin is rinsed well.
10. the preparation method of the phenylethylene resin series as described in claim 8 or 9, is characterized in that: in post-crosslinking reaction process, adopts liquor ferri trichloridi or aluminum trichloride solution as catalyzer.
The preparation method of 11. phenylethylene resin series as claimed in claim 8 or 9, is characterized in that: in post-crosslinking reaction process, adopts liquor zinci chloridi or Cupric Chloride Solution as catalyzer.
The preparation method of 12. phenylethylene resin series as claimed in claim 9, is characterized in that: in post-crosslinking reaction process, adopts ethylene dichloride or liquid alcohol to make swelling agent, adopts liquor ferri trichloridi or aluminum trichloride solution as catalyzer; Its 3rd step: again adding when catalyst solution to temperature is elevated to swelling agent boiling point, continues to stir; Keep temperature and add edible iodized salt and/or sugar defervescence, add-on is 0.5 to 1.5 times of catalyzer; 4th step: continue to stir, two hours time, then add sodium hydroxide, temperature of charge raises suddenly, stops adding sodium hydroxide, adds water cooling, and reactive material released from reaction container bottom when temperature raises 30 DEG C; 5th step: rinsed well by reacted resin, the resin adopting liquor ferri trichloridi to obtain is redness, garnet or black.
The preparation method of 13. phenylethylene resin series as claimed in claim 7, the method embeds metallic element X in polystyrene gel-type anion exchange resin skeleton, it is characterized in that: in polystyrene gel-type anion exchange resin post-crosslinking reaction process, adopt ethylene dichloride or liquid alcohols as swelling agent, the metallic element X compound as catalyzer uses in the form of a solution; The first step: swelling agent makes resin fully swelling at normal temperatures, resin is resin quality with the ratio of swelling agent add-on: swelling agent volume, i.e. the ratio of Kg/L, and its ratio is 1:6 to 1:60; Soak time is 8 hours to 120 hours; Second step: add metal X compound solution catalyzer when swelling agent is heated to boiling point, temperature is kept to add sodium hydroxide after four hours, make resin suddenly be warming up to 92 to 96 DEG C and produce fierce boiling, metallic element X reactant heat up and in fierce boiling process embedded resin skeleton carbochain in, be cooled to normal temperature immediately.
The preparation method of 14. phenylethylene resin series as claimed in claim 13, it is characterized in that: in second step, the catalyst solution added accounts for swellable resins ratio 1/10 and fully mixing, heat to during swelling agent boiling point and stop heating, keep temperature four hours, add again and account for the sodium hydroxide that resin reaction object amasss 20%, stop heating up when making resin be warming up to the boiling of reactant fierceness, immediately add the edible iodized salt accounting for resin reaction object 20% and/or the sugar accounting for resin reaction object 20%, rapid cooling, and release from reactor.
The preparation method of 15. phenylethylene resin series as described in claim 13 or 14, is characterized in that: in post-crosslinking reaction process, adopt liquor ferri trichloridi as catalyzer, or aluminum trichloride solution is as catalyzer.
The preparation method of 16. phenylethylene resin series as described in claim 13 or 14, is characterized in that: in post-crosslinking reaction process, adopt Cupric Chloride Solution, or liquor zinci chloridi is as catalyzer.
The purposes of 17. phenylethylene resin series according to any one of claim 1 or 7, it is characterized in that: the aperture 0-200nm of the phenylethylene resin series of employing, pore volume and specific surface area are not limit; The Y point of the trivalent metallic element embedded in its carbochain is by OH occupy-place and/or by the occupy-place of monose loop chain and/or by the functional group occupy-place with contraposition valence state; Its purposes is for blood perfusion device sorbent material, or is used as oral resin sorbent; The virulence factor in resin pore diameter range by Peripheral Circulation system or gi system adsorption removal particle diameter.
The purposes of 18. phenylethylene resin series as claimed in claim 17, it is characterized in that: when making sorbent material for blood perfusion device and using, select according to the valence state attribute of virulence factor of absorption and particle diameter and there is contraposition valence state functional group, and the resin being suitable for aperture is to fill blood perfusion device; The mode of filling is that a kind of resin of pore diameter range loads a tank, and blood perfusion device is according to the material valence state attributive classification in in-built resin aperture and Y site; Or arrange according to the direction along blood flow warp, the large resin filling in aperture is at upstream position; Be loaded in perfusion device according to the order layering that aperture is descending is mixed, and according to the material valence state delamination classification that the element or functional group that occupy Y point have.
The purposes of 19. phenylethylene resin series as claimed in claim 17, is characterized in that: use as oral adsorbent agent, the different resin valence state attribute that different pore size and Y point have, respectively or be mixed in proportion and be packaged in medicinal slow releasing capsule.
CN201310347458.XA 2013-08-01 2013-08-12 Novel structure product, preparation method and use of styrenic resin Active CN103483487B (en)

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CN201510156544.1A CN104815628B (en) 2013-08-12 2013-08-12 A kind of purposes of modified phenylethylene-divinylbenzene macroporous absorbent resin
CN201510291604.0A CN104923185B (en) 2013-08-12 2013-08-12 Medical polymeric adsorbent for removing H N macromoleculars virus
CN201510120761.5A CN104667897B (en) 2013-08-12 2013-08-12 For adsorbing high endotoxic phenylethylene resin series in blood
CN201310347458.XA CN103483487B (en) 2013-08-01 2013-08-12 Novel structure product, preparation method and use of styrenic resin
CN201510291602.1A CN104941607B (en) 2013-08-12 2013-08-12 Styrene resin adsorption agent for clearing high beta2 microglobulin in blood
CN201510120428.4A CN104689803B (en) 2013-08-12 2013-08-12 For adsorbing the phenylethylene resin series of hepatitis viruse in blood
CN201510291617.8A CN104857015A (en) 2013-08-12 2013-08-12 Styrene type novel-structure adsorption resin for de-addiction and detoxification
CN201510120484.8A CN104667896B (en) 2013-08-12 2013-08-12 For removing the phenylethylene resin series adsorbent of high triglyceride in blood
CN201510291618.2A CN104922147A (en) 2013-08-12 2013-08-12 New structure medical resin for eliminating high cholesterol
CN201510291616.3A CN104887700A (en) 2013-08-12 2013-08-12 Medical adsorptive resin for eliminating syphilis and sexual disease pathogenic factors
CN201510291587.0A CN104887699A (en) 2013-08-12 2013-08-12 Medical adsorptive resin for clearing away factors blocking nerve conduction
CN201510120605.9A CN104689804B (en) 2013-08-12 2013-08-12 For adsorbing the phenylethylene resin series of AIDS virus molecule in blood
PCT/CN2014/000203 WO2015014091A1 (en) 2013-08-01 2014-03-06 New structure product, preparation method and use of styrenic resin

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CN201310328855.2 2013-08-01
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CN201310338015 2013-08-06
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CN201510120761.5A Division CN104667897B (en) 2013-08-12 2013-08-12 For adsorbing high endotoxic phenylethylene resin series in blood
CN201510120605.9A Division CN104689804B (en) 2013-08-12 2013-08-12 For adsorbing the phenylethylene resin series of AIDS virus molecule in blood
CN201510291618.2A Division CN104922147A (en) 2013-08-12 2013-08-12 New structure medical resin for eliminating high cholesterol
CN201510291587.0A Division CN104887699A (en) 2013-08-12 2013-08-12 Medical adsorptive resin for clearing away factors blocking nerve conduction
CN201510291616.3A Division CN104887700A (en) 2013-08-12 2013-08-12 Medical adsorptive resin for eliminating syphilis and sexual disease pathogenic factors
CN201510291604.0A Division CN104923185B (en) 2013-08-12 2013-08-12 Medical polymeric adsorbent for removing H N macromoleculars virus
CN201510156544.1A Division CN104815628B (en) 2013-08-12 2013-08-12 A kind of purposes of modified phenylethylene-divinylbenzene macroporous absorbent resin
CN201510291617.8A Division CN104857015A (en) 2013-08-12 2013-08-12 Styrene type novel-structure adsorption resin for de-addiction and detoxification
CN201510120428.4A Division CN104689803B (en) 2013-08-12 2013-08-12 For adsorbing the phenylethylene resin series of hepatitis viruse in blood
CN201510291602.1A Division CN104941607B (en) 2013-08-12 2013-08-12 Styrene resin adsorption agent for clearing high beta2 microglobulin in blood
CN201510120484.8A Division CN104667896B (en) 2013-08-12 2013-08-12 For removing the phenylethylene resin series adsorbent of high triglyceride in blood

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