CN104437360A - Preparation method of resin carbon for blood purification - Google Patents
Preparation method of resin carbon for blood purification Download PDFInfo
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- CN104437360A CN104437360A CN201410576607.4A CN201410576607A CN104437360A CN 104437360 A CN104437360 A CN 104437360A CN 201410576607 A CN201410576607 A CN 201410576607A CN 104437360 A CN104437360 A CN 104437360A
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- China
- Prior art keywords
- preparation
- resin carbon
- blood purification
- divinylbenzene
- microspheres
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 239000011347 resin Substances 0.000 title claims abstract description 42
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000008280 blood Substances 0.000 title claims abstract description 26
- 210000004369 blood Anatomy 0.000 title claims abstract description 26
- 238000000746 purification Methods 0.000 title claims abstract description 22
- 239000004005 microsphere Substances 0.000 claims abstract description 36
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical class C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 20
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 10
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 5
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 239000004088 foaming agent Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 230000008961 swelling Effects 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002841 Lewis acid Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005662 Paraffin oil Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 2
- 229960001939 zinc chloride Drugs 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 241001566735 Archon Species 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000008081 blood perfusion Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 108010088751 Albumins Proteins 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 102000016943 Muramidase Human genes 0.000 description 2
- 108010014251 Muramidase Proteins 0.000 description 2
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 2
- 102000003982 Parathyroid hormone Human genes 0.000 description 2
- 108090000445 Parathyroid hormone Proteins 0.000 description 2
- 208000001647 Renal Insufficiency Diseases 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 201000006370 kidney failure Diseases 0.000 description 2
- 239000004325 lysozyme Substances 0.000 description 2
- 229960000274 lysozyme Drugs 0.000 description 2
- 235000010335 lysozyme Nutrition 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000000199 parathyroid hormone Substances 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 206010027336 Menstruation delayed Diseases 0.000 description 1
- -1 and pollute little Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RBSPDPOMMJRYQE-UHFFFAOYSA-N benzene;nitric acid Chemical compound O[N+]([O-])=O.C1=CC=CC=C1 RBSPDPOMMJRYQE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- External Artificial Organs (AREA)
Abstract
The invention discloses a preparation method of resin carbon for blood purification. The preparation method comprises the following steps: preparing chloromethylated styrene-divinylbenzene microspheres from p-chloromethyl styrene monomers and divinylbenzene monomers; preparing polystyrene-divinylbenzene microspheres from the chloromethylated styrene-divinylbenzene microspheres; dipping the polystyrene-divinylbenzene microspheres by using a zinc-chloride solution to obtain dipped microspheres; and carbonizing the dipped microspheres, and activating the dipped microspheres after the carbonizing so as to obtain a finished product. The preparation method disclosed by the invention has the obvious effects that the resin carbon with the excellent absorbing effect for middle molecules can be prepared and obtained at relatively low temperature and within shorter time, the preparation process is simple, the pollution is slight, the product yield is high and the purity is high.
Description
Technical field
The present invention relates to blood purification material, be specifically related to a kind of preparation method of the resin carbon for blood purification.
Background technology
Renal failure in late period client need sustains life by dialysis, the small-molecule substance in blood effectively can be removed by dialysis membrane, but the testing result of modern medical service means makes people recognize, and more middle molecular substance (0.5 ~ 60kDa) is the key substance affecting patient health in addition, and these middle molecular substances are difficult to effective removal by dialysis; In maintenance Renal Failure Patients life, no matter adopt haemodialysis or blood perfusion, effectively can remove medium molecular substance has become the whether effectively new criterion of measurement methods for the treatment of.
Resin carbon is as the one of active carbon, and because its purity is high, mechanical strength is good, and specific area is large, is widely used in biomedicine field.Resin carbon after coating is as the effective wide spectrum adsorbent of one, apply very extensive clinically, but due to preparation technology and raw-material relation, the inner pore-size distribution of resin carbon of coating is very wide, possesses the toxicant of resin carbon easy adsorb macromolecules amount when blood perfusion of more macropore, as the middle molecule toxins in uremic patient body is mixed group (MMS), parathormone (PTH) and B2M (β 2-MG) etc.; But the resin carbon after coating is after the large molecular toxicity material that absorption is more, greatly can reduce, effectively can not remove the noxious material in uremic patient blood to the adsorption effect of medium molecular substance.
The polystyrene-based microballoon of superhigh cross-linking degree is widely used in being separated adsorbing domain always, and it is simple that it possesses preparation method, and internal holes gauge structure such as easily to control at the feature; But the hydrophobicity of polystyrene is comparatively strong, be easy to adsorb the macromolecular substances such as protein a large amount of in blood, and in these macromolecular substances, have a lot of material (such as albumin) to be indispensable benefit materials in human body; Therefore the polystyrene-based microballoon of superhigh cross-linking degree is seldom directly applied separately in blood perfusion field.
Someone proposed a kind of preparation method with the active carbon of excellent Middle molecule absorption property afterwards, its process mainly obtains the styrene-divinylbenzene microballoon of secondary cross-linking through steps such as Archon synthesis, chloromethylation, Friedel-crafts reactions, and carry out carbonizing and activating on this basis, adopt the resin carbon that the method is obtained, there is preferably Middle molecule absorption property and good pore-size distribution, but used the internationally recognized carcinogen such as chloromethyl ether, nitrobenzene in the method process as crosslinking agent or organic solvent.
Summary of the invention
For solving above technical problem, the invention provides a kind of preparation method of the resin carbon for blood purification.
Technical scheme is as follows:
For a preparation method for the resin carbon of blood purification, its key is to carry out according to the following steps:
Step one, be oil mixture by p-chloromethyl styrene monomer and divinylbenzene monomers mixed preparing, add benzoyl peroxide, pore-foaming agent and stabilizing agent simultaneously, adopt suspension polymerization, prepare crosslinked chloromethylated styrene-divinylbenzene microspheres;
Step 2, described chloromethylated styrene-divinylbenzene microspheres is dropped into sweller carry out swelling, then add Lewis acid, be separated after reaction, cleaning obtains the polystyrene-divinylbenzene microspheres that is cross-linked;
Step 3, described polystyrene-divinylbenzene microspheres liquor zinci chloridi to be flooded, obtain flooding microballoon;
Step 4, described dipping microballoon is put into retort, pass into inert gas, heat up dehydration, then continue intensification and carbonize, and obtains carbonizing microballoon;
Step 5, continued in an inert atmosphere described charing microballoon, heat up activation, obtains finished product.
In above-mentioned steps one, p-chloromethyl styrene monomer and divinylbenzene are oil mixture according to the mass ratio mixed preparing of 1:1 ~ 2, the addition of described benzoyl peroxide is 0.5 ~ 1%wt of oil mixture quality, the addition of described pore-foaming agent is less than or equal to the 40%wt of oil mixture quality, and the addition of described stabilizing agent is 3 ~ 10%wt of oil mixture quality.
In above-mentioned steps one, described pore-foaming agent be one in toluene, naphthalene, paraffin oil, octane, hexadecane, two kinds, three kinds, four kinds or five kinds, described stabilizing agent is polyvinyl alcohol.
In above-mentioned steps two, swelling time is the addition of 2 ~ 4h, Lewis acid is described chloromethylated styrene-divinylbenzene microspheres quality 20 ~ 30%wt, is warming up to 80 ~ 100 DEG C after adding Lewis acid, reaction 6 ~ 8h, separation, cleaning obtain described polystyrene-divinylbenzene microspheres.
In above-mentioned steps two, described sweller is the one in pyridine, DMF, dimethyl sulfoxide (DMSO).
In above-mentioned steps three, liquor zinci chloridi concentration is 10 ~ 30%wt, and dip time is 2 ~ 4h, and impregnating ratio is 1:2.5 ~ 4.
In above-mentioned steps four, after described dipping microballoon is put into retort, with ramp to 150 ~ 250 DEG C of 5 DEG C/min, dehydration 2 ~ 4h; Continue to be warming up to 300 ~ 400 DEG C again to carry out, 1 ~ 3h.
In above-mentioned steps five, be warming up to 450 ~ 600 DEG C, activation 2 ~ 3h.
In above-mentioned steps two, drop into sweller again after described chloromethylated styrene-divinylbenzene microspheres water or acetone being cleaned and carry out swelling.
In above-mentioned steps two, Lewis acid is the one in zinc chloride, aluminium chloride, iron chloride.
Through the resin carbon for blood purification that above-mentioned steps obtains, good sphericity, specific area (BET) can reach 500 ~ 2000m
2/ g, aperture is adjustable within the scope of 2 ~ 10nm, and bulk density is controlled within the scope of 0.25 ~ 0.5g/ml, and pore volume is at more than 0.73ml/g;
Below in conjunction with test example, the invention will be further described:
The resin carbon I adopting the inventive method to obtain respectively and the resin carbon II adopting existing method to obtain carry out external Middle molecule adsorption test, and experiment condition follows single-factor variable principle, measures resin carbon I and resin carbon II couple of VB respectively
12, lysozyme and bovine serum albumin(BSA) adsorption rate, wherein VB
12be medium molecular substance with lysozyme, ox blood albumin is macromolecular substances;
Existing methodical operating procedure is: a, styrene-divinylbenzene copolymer, chloromethyl ether and zinc chloride are mixed with chlorine ball; B, by chlorine ball obtained for step a and the mixing of nitric acid benzene, and add aluminium chloride and prepare Archon; C, Archon obtained for step b is cleaned after heated oxide in atmosphere; D, again through heating charing, the obtained resin carbon II of activation.
Adsorption rate represents with the percentage being accounted for total amount by the amount of adsorbing, resin carbon I and resin carbon II and absorption property as shown in table 1:
The absorption property of table 1 resin carbon I and resin carbon II
As can be seen from Table 1, the resin carbon adopting the inventive method to prepare, has better Middle molecule absorption property, not obvious to macromolecular suction-operated.
Beneficial effect: adopt the present invention to be used for the preparation method of the resin carbon of blood purification, in lower temperature and resin carbon Middle molecule to good adsorbent effect in the shorter time, can be prepared, preparation process is simple, add without carcinogen, and pollute little, product yield is high, purity is high; Reaction temperature is low, and the reaction time is short.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
For a preparation method for the resin carbon of blood purification, carry out according to the following steps:
Step one, be oil mixture by p-chloromethyl styrene monomer and divinylbenzene according to the mass ratio mixed preparing of 1:1, add the benzoyl peroxide of this oil mixture quality 0.5%wt, the pore-foaming agent of this oil mixture quality 2%wt and the stabilizing agent of this oil mixture quality 3%wt simultaneously; Adopt suspension polymerization, prepare crosslinked chloromethylated styrene-divinylbenzene microspheres;
Described pore-foaming agent is any one or any two kinds in toluene, naphthalene, paraffin oil, octane, hexadecane, and described stabilizing agent is polyvinyl alcohol;
Step 2, described chloromethylated styrene-divinylbenzene microspheres is washed rear input sweller carry out swelling, described sweller is pyridine, swelling time is 2h, add the zinc chloride of described chloromethylated styrene-divinylbenzene microspheres quality 20%wt again, be warming up to 80 DEG C, reaction 6h, is separated, cleans the polystyrene-divinylbenzene microspheres obtaining being cross-linked;
Step 3, be the liquor zinci chloridi dipping 2h of 10%wt by described polystyrene-divinylbenzene microspheres solution concentration, impregnating ratio is 1:2.5, obtains flooding microballoon;
Step 4, described dipping microballoon is put into retort, pass into inert gas, with the ramp to 150 DEG C of 5 DEG C/min, dehydration 2h; Continue again to be warming up to 300 DEG C, charing 1h, obtain carbonizing microballoon;
Step 5, described charing microballoon continued to be warming up to 450 DEG C in an inert atmosphere, activation 2h, obtains finished product.
The specific area (BET) of the resin carbon that the present embodiment obtains is 500m
2/ g, aperture is 2nm, and bulk density is 0.25g/ml, and pore volume is 0.74ml/g.
Embodiment 2:
For a preparation method for the resin carbon of blood purification, carry out according to the following steps:
Step one, be oil mixture by p-chloromethyl styrene monomer and divinylbenzene according to the mass ratio mixed preparing of 1:2, add the benzoyl peroxide of this oil mixture quality 1%wt, the pore-foaming agent of this oil mixture quality 25%wt and the stabilizing agent of this oil mixture quality 10%wt simultaneously; Adopt suspension polymerization, prepare crosslinked chloromethylated styrene-divinylbenzene microspheres;
Described pore-foaming agent is any three kinds or any four kinds in toluene, naphthalene, paraffin oil, octane, hexadecane, and described stabilizing agent is polyvinyl alcohol;
Step 2, by described chloromethylated styrene-divinylbenzene microspheres acetone clean after drop into sweller carry out swelling, described sweller is dimethyl sulfoxide (DMSO), swelling time is 4h, add the iron chloride of described chloromethylated styrene-divinylbenzene microspheres quality 30%wt again, be warming up to 100 DEG C, reaction 8h, is separated, cleans the polystyrene-divinylbenzene microspheres obtaining being cross-linked;
Step 3, be the liquor zinci chloridi dipping 4h of 30%wt by described polystyrene-divinylbenzene microspheres solution concentration, impregnating ratio is 1:4, obtains flooding microballoon;
Step 4, described dipping microballoon is put into retort, pass into inert gas, with the ramp to 250 DEG C of 5 DEG C/min, dehydration 4h; Continue again to be warming up to 400 DEG C, charing 3h, obtain carbonizing microballoon;
Step 5, described charing microballoon continued to be warming up to 600 DEG C in an inert atmosphere, activation 3h, obtains finished product.
The specific area (BET) of the resin carbon that the present embodiment obtains is 2000m
2/ g, aperture is 10nm, and bulk density is 0.5g/ml, and pore volume is 0.77g.
Embodiment 3:
For a preparation method for the resin carbon of blood purification, carry out according to the following steps:
Step one, be oil mixture by p-chloromethyl styrene monomer and divinylbenzene according to the mass ratio mixed preparing of 1:1.5, add the benzoyl peroxide of this oil mixture quality 0.8%wt, the pore-foaming agent of this oil mixture quality 40%wt and the stabilizing agent of this oil mixture quality 7%wt simultaneously; Adopt suspension polymerization, prepare crosslinked chloromethylated styrene-divinylbenzene microspheres;
Toluene, naphthalene, paraffin oil, octane and hexadecane are mixed to get described pore-foaming agent according to the mass ratio of 2:3:1.5:0.8:0.5, and described stabilizing agent is polyvinyl alcohol;
Step 2, described chloromethylated styrene-divinylbenzene microspheres water or acetone are cleaned after drop into sweller and carry out swelling, described sweller is N, dinethylformamide, swelling time is 3h, add the aluminium chloride of described chloromethylated styrene-divinylbenzene microspheres quality 25%wt again, be warming up to 90 DEG C, reaction 7h, be separated, clean the polystyrene-divinylbenzene microspheres obtaining being cross-linked;
Step 3, be the liquor zinci chloridi dipping 3h of 20%wt by described polystyrene-divinylbenzene microspheres solution concentration, impregnating ratio is 1:3, obtains flooding microballoon;
Step 4, described dipping microballoon is put into retort, pass into inert gas, with the ramp to 210 DEG C of 5 DEG C/min, dehydration 3h; Continue again to be warming up to 360 DEG C, charing 2h, obtain carbonizing microballoon;
Step 5, described charing microballoon continued to be warming up to 535 DEG C in an inert atmosphere, activation 2.5h, obtains finished product.
The specific area (BET) of the resin carbon that the present embodiment obtains is 1088m
2/ g, aperture is 5.6nm, and bulk density is 0.37g/ml, and pore volume is 0.82ml/g.
Claims (10)
1., for a preparation method for the resin carbon of blood purification, it is characterized in that carrying out according to the following steps:
Step one, be oil mixture by p-chloromethyl styrene monomer and divinylbenzene monomers mixed preparing, add benzoyl peroxide, pore-foaming agent and stabilizing agent simultaneously, adopt suspension polymerization, prepare crosslinked chloromethylated styrene-divinylbenzene microspheres;
Step 2, described chloromethylated styrene-divinylbenzene microspheres is dropped into sweller carry out swelling, then add Lewis acid, be separated after reaction, cleaning obtains the polystyrene-divinylbenzene microspheres that is cross-linked;
Step 3, described polystyrene-divinylbenzene microspheres liquor zinci chloridi to be flooded, obtain flooding microballoon;
Step 4, described dipping microballoon is put into retort, pass into inert gas, heat up dehydration, then continue intensification and carbonize, and obtains carbonizing microballoon;
Step 5, continued in an inert atmosphere described charing microballoon, heat up activation, obtains finished product.
2. the preparation method of the resin carbon for blood purification according to claim 1, it is characterized in that: in described step one, p-chloromethyl styrene monomer and divinylbenzene are oil mixture according to the mass ratio mixed preparing of 1:1 ~ 2, the addition of described benzoyl peroxide is 0.5 ~ 1%wt of oil mixture quality, the addition of described pore-foaming agent is less than or equal to the 40%wt of oil mixture quality, and the addition of described stabilizing agent is 3 ~ 10%wt of oil mixture quality.
3. the preparation method of the resin carbon for blood purification according to claim 1 and 2, it is characterized in that: in described step one, described pore-foaming agent be one in toluene, naphthalene, paraffin oil, octane, hexadecane, two kinds, three kinds, four kinds or five kinds, described stabilizing agent is polyvinyl alcohol.
4. the preparation method of the resin carbon for blood purification according to claim 1, it is characterized in that: in described step 2, swelling time is 2 ~ 4h, the addition of Lewis acid is described chloromethylated styrene-divinylbenzene microspheres quality 20 ~ 30%wt, 80 ~ 100 DEG C are warming up to after adding Lewis acid, reaction 6 ~ 8h, separation, cleaning obtain described polystyrene-divinylbenzene microspheres.
5. the preparation method of the resin carbon for blood purification according to claim 1 or 4, is characterized in that: in described step 2, and described sweller is the one in pyridine, DMF, dimethyl sulfoxide (DMSO).
6. the preparation method of the resin carbon for blood purification according to claim 1,2 or 4, is characterized in that: in described step 3, and liquor zinci chloridi concentration is 10 ~ 30%wt, and dip time is 2 ~ 4h.
7. the preparation method of the resin carbon for blood purification according to claim 1, is characterized in that: in described step 4, after described dipping microballoon is put into retort, with ramp to 150 ~ 250 DEG C of 5 DEG C/min, and dehydration 2 ~ 4h; Continue again to be warming up to 300 ~ 400 DEG C, charing 1 ~ 3h.
8. the preparation method of the resin carbon for blood purification according to claim 1,2,4 or 7, is characterized in that: in described step 5, is warming up to 450 ~ 600 DEG C, activation 2 ~ 3h.
9. the preparation method of the resin carbon for blood purification according to claim 1, is characterized in that: in described step 2, drops into sweller again and carry out swelling after described chloromethylated styrene-divinylbenzene microspheres water or acetone being cleaned.
10. the preparation method of the resin carbon for blood purification according to claim 1,2,4,7 or 9, is characterized in that: in described step 2, and Lewis acid is the one in zinc chloride, aluminium chloride, iron chloride.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN112452308A (en) * | 2020-12-09 | 2021-03-09 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN117486210A (en) * | 2023-11-01 | 2024-02-02 | 玉门朗天生物科技有限公司 | Production method of resin-based activated carbon and resin-based activated carbon |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391407A (en) * | 2011-09-26 | 2012-03-28 | 南京大学 | Ultrahigh crosslinked resin for separating and recovering medium and high concentration volatile organic compounds (VOCs), and preparation method and application of resin |
| CN102941070A (en) * | 2012-11-30 | 2013-02-27 | 南京大学 | Polyethylene-methacrylic acid-polyethylene polyamine fiber and method for preparing same |
| CN103301890A (en) * | 2013-06-26 | 2013-09-18 | 东南大学 | Selective strong-base anion exchange resin and preparation method thereof |
| CN103483487A (en) * | 2013-08-01 | 2014-01-01 | 于杰 | Novel structure product, preparation method and use of styrenic resin |
| CN103801406A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method for titanium silicon molecular sieve-resin composite catalyst |
-
2014
- 2014-10-24 CN CN201410576607.4A patent/CN104437360B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391407A (en) * | 2011-09-26 | 2012-03-28 | 南京大学 | Ultrahigh crosslinked resin for separating and recovering medium and high concentration volatile organic compounds (VOCs), and preparation method and application of resin |
| CN103801406A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method for titanium silicon molecular sieve-resin composite catalyst |
| CN102941070A (en) * | 2012-11-30 | 2013-02-27 | 南京大学 | Polyethylene-methacrylic acid-polyethylene polyamine fiber and method for preparing same |
| CN103301890A (en) * | 2013-06-26 | 2013-09-18 | 东南大学 | Selective strong-base anion exchange resin and preparation method thereof |
| CN103483487A (en) * | 2013-08-01 | 2014-01-01 | 于杰 | Novel structure product, preparation method and use of styrenic resin |
Non-Patent Citations (4)
| Title |
|---|
| JIRI URBAN ET AL.: "Hypercrosslinking: New approach to porous polymer monolithic capillary columns with large surface area for the highly efficient separation of small molecules", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| N´URIA FONTANALS ET AL.: "Monodisperse, hypercrosslinked polymer microspheres as tailor-made sorbents for highly efficient solid-phase extractions of polar pollutants from water samples", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| ZHAOLIAN ZHU ET AL.: "Preparation and characterization of highly mesoporous spherical activated carbons from divinylbenzene-derived polymer by ZnCl2 activation", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| ZHIMING XIE: "Preparation and characterization of hypercrosslinked resins with bimodal pore size distribution and controllable microporosity", 《MATERIALS LETTERS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| CN112452308A (en) * | 2020-12-09 | 2021-03-09 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN112452308B (en) * | 2020-12-09 | 2022-10-25 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN117486210A (en) * | 2023-11-01 | 2024-02-02 | 玉门朗天生物科技有限公司 | Production method of resin-based activated carbon and resin-based activated carbon |
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Denomination of invention: Preparation method of resin charcoal for blood purification Effective date of registration: 20231214 Granted publication date: 20170606 Pledgee: Societe Generale Limited by Share Ltd. Chongqing branch Pledgor: CHONGQING XIERKANG BLOOD PURIFICATION EQUIPMENT RESEARCH DEVELOPMENT CO.,LTD. Registration number: Y2023500000103 |