CN101058068A - Macroporous adsorption resin special used for separating antibiotic and its preparation method - Google Patents
Macroporous adsorption resin special used for separating antibiotic and its preparation method Download PDFInfo
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- CN101058068A CN101058068A CN 200710069135 CN200710069135A CN101058068A CN 101058068 A CN101058068 A CN 101058068A CN 200710069135 CN200710069135 CN 200710069135 CN 200710069135 A CN200710069135 A CN 200710069135A CN 101058068 A CN101058068 A CN 101058068A
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Abstract
The invention relates to a big hole absorbent resin for separating antibiotics, with St-DVB as the material, using 2-4 functional integral and gallant for secondary dual net interconnected polymer reaction under the conditions with peroxy initiator, water and inorganic salt. The proportion ratio of the St-DVB is phenylethene, 80% diphenylethyllene, benzoyl peroxide, porous agent, dope and distilled water. The secondary dual net interconnected polymer reaction proportion comprises the St-DVB, 2-4 functional integral, peroxy initiator, stabilizer and distilled water. The synthetic resin absorption volume for abomacetin is 185ku/g, being 140% of the existing ones, with an increase of 70-90% of coloring matter removal efficiency.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of polymeric adsorbent and preparation thereof, for a kind of equipment that is applied to pharmacy industry and preparation method thereof, specifically is macroporous absorbent resin of a kind of antibiotic separate, dedicated and preparation method thereof especially.
Background technology
The synthetic method of macroporous absorbent resin mainly includes the pore-foaming agent cross-linked polymeric that participates in and two kinds of methods such as secondary cross-linking of reacting based on functional group.The former is as U.S. Rohrn ﹠amp; Series such as Amberlite XAD4, XAD7 that Haas company produces and XAD16, domestic also have similar products such as LS16 and a LS18 etc.; The latter such as domestic resin NKA, XDA and H series etc.Facts have proved that the pore structure uniformity of the resin that the cross-linked polymeric method that adopting has pore-foaming agent to participate in is synthesized is relatively poor, and adopts the aperture of the secondary cross-linking method synthetic resin that reacts based on functional group less relatively.This two resinoid is used for from zymotic fluid isolated molecule amount when the antibiotic of 500-1200 scope, and its equilibrium adsorption capacity can only reach 100-130ku/g usually.On the other hand, this two resinoid also has certain adsorption capacity to being present in impurity such as pigment in the zymotic fluid and albumen, thereby cause the antibiotic concentration of separate targets thing and all basic demands of inaccessible follow-up separation process of purity in its stripping liquid, this perhaps become this technology at present as yet not at home the erythromycin production field obtain industrialized major reason.
It is to prepare the conventional method of passing through cross-linked network polymer (IEN) mutually that two nets pass through cross-linking polymerization mutually; see in the synthetic field of ion-exchanger to be used for the synthetic of synthetic chelating resin and amphoteric ion-exchange resin, as document (SCI, 1994 more; 09,1310).Do not see at present the bibliographical information that is used for macroporous absorbent resin.
From the conventional method of streptomyces erythreus zymotic fluid separate red mycin is the butyl acetate extraction process, and the greatest drawback of this technology is exactly separative efficiency lower (≤68%), loss of extractant and energy consumption is higher, contaminated wastewater is serious etc.Adopt resin absorption technique to replace extraction process then to be expected to overcome these defectives, but require the adsorption capacity of resin and ability removed in the selection of pigment higher relatively, inaccessible this requirement of common polymeric adsorbent.
Summary of the invention
The objective of the invention is to provides a kind of macroporous absorbent resin that is applicable to the antibiotic separate, dedicated at from the basic demand of streptomyces erythreus zymotic fluid separate red mycin to adsorption and separation material, discloses its preparation method simultaneously.
The present invention uses for reference passes through improvement and the raising that the cross-linked network synthetic technology is used for the polymeric adsorbent performance mutually, on the basis of the synthetic polymeric adsorbent of conventional crosslinking copolymerization, pass through cross-linking polymerization mutually by the two nets of secondary and reach and improve resin pore structure uniformity, give the suitable polarity inner surface of resin, improve resin to the adsorption capacity of separate targets thing and purpose optionally simultaneously according to the antibiotic polar requirement of separate targets thing.
The macroporous absorbent resin of antibiotic separate, dedicated of the present invention is characterized in adopting 2～4 kinds of specific function monomers and crosslinking agent under peroxide initiator, water and inorganic salts existence condition, carries out the two nets of secondary with styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) and passes through the crosslinking copolymerization reaction mutually and synthesize; The prescription of styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) is by weight:
5～20 parts of styrene (St)
80～100 parts of 80% divinylbenzenes (DVB)
0.5～2.5 part of dibenzoyl peroxide (BPO)
50～150 parts of pore-foaming agents (toluene, atoleine and gasoline one)
1～5 part in gelatin
300～600 parts of distilled water
The chemical formula of above-mentioned crosslinking agent is: CH
2=CHR
4CH=CH
2
This resin reaches 185ku/g to the equilibrium adsorption capacity of erythromycin in the streptomyces erythreus fermentation cleaner liquid, is 140% of conventional polymeric adsorbent, and its selection to pigment in the zymotic fluid is removed the more conventional resin of ability and improved 70-90%.Replace butyl acetate extraction process separate red mycin with it, have separative efficiency and resource utilization height, no loss of extractant, energy consumption is low and the lighter many advantages of contaminated wastewater.
The preparation method of macroporous adsorption resin special used for separating antibiotic of the present invention is following steps:
1, carries out conventional suspension polymerization according to the prescription of above-mentioned styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) and promptly obtain styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon), adopt methods such as steam distillation thoroughly to remove pore-foaming agent again;
2, the two nets of secondary pass through the prescription of crosslinking copolymerization reaction mutually and are by weight:
50～100 parts of St-DVB Archons
5～50 parts of 2～4 kinds of function monomers
0.5～5 part of peroxide initiator
10～50 parts of inert diluents
5～20 parts of stabilizing agents
100～300 parts of distilled water
Carry out the two nets of secondary according to prescription and the conventional suspension polymerisation condition of reference and pass through the crosslinking copolymerization reaction mutually, promptly obtain macroporous adsorption resin special used for separating antibiotic with hot water or cold water's cyclic washing again.
3, the chemical formula of above-mentioned 2～4 kinds of function monomers, inert diluent and crosslinked used crosslinking agent is:
Function monomer CH
2=CR
1R
2
Inert diluent C
nH
mAnd C
qH
pCOOR
3The material equal proportion mix
Crosslinking agent CH
2=CHR
4CH=CH
2
N, m, q and p are 2～10 positive integer in the formula, R
1, R
2Be H, CH
3, COOC
nH
m, COOH, CN or C
6H
5, R
3Be C
nH
m, R
4Be C
6H
4, CONH-CH
2-HNCO or COOC
2H
4OOC.
The present invention has following characteristics:
1, the synthetic method of used styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) is same as the synthesis technique and the condition of conventional macroporous absorbent resin, and technical maturity, condition are convenient to control, constant product quality.
2, the two nets of secondary pass through mutually that crosslinking copolymerization reacts the kind of used function monomer and factors such as characteristic that impurities in the antibiotic molecular weight of separate targets thing, molecular structure and polarity size and the zymotic fluid is abideed by by consumption system are determined, thereby can synthesize the special-purpose antibiotic parting material with high-adsorption-capacity and high selectivity targetedly.
3, adopt the two nets of this secondary to pass through cross-linked adsorbing resin mutually and replace the butyl acetate extraction process, have separative efficiency and selectivity height, resource utilization height, reduce solvent and energy resource consumption, alleviate the significant advantage of waste water environmental pollution from streptomyces erythreus fermentation cleaner liquid separate red mycin.
The present invention relates to adopt the two nets of secondary to pass through crosslinking copolymerization reaction synthetic antibiotic macroporous adsorbent resin special for separating adsorption method mutually, be characterized in structural parameters such as the specific area of institute's synthetic resin and average pore size mainly by the synthesis condition decision of St-DVB Archon, it then mainly passes through characteristic, consumption and the copolyreaction conditional decision thereof that crosslinking copolymerization reacts used function monomer, crosslinking agent and diluent by the two nets of secondary mutually to antibiotic adsorption capacity of separate targets thing and separation selectivity.Institute's synthetic resin reaches 185ku/g to the equilibrium adsorption capacity of erythromycin in the streptomyces erythreus fermentation cleaner liquid, is 140% of conventional polymeric adsorbent, and its selection to pigment in the zymotic fluid is removed the more conventional resin of ability and improved 70-90%.
The specific embodiment
1, most preferred embodiment
Passing through the used St-DVB macropore of cross-linked adsorbing resin copolymerization bead (St-DVB Archon) optimum formula by weight mutually according to the two nets of synthesis of erythromycin separate, dedicated secondary of the present invention is:
5～10 parts of styrene (St)
90～95 parts of divinylbenzenes (DVB, content 80%)
1～3 part of dibenzoyl peroxide (BPO)
80～120 parts in pore-foaming agent toluene, atoleine or gasoline etc.
2～2.5 parts in gelatin
400～500 parts of distilled water
Carry out conventional suspension polymerization according to optimum formula and promptly obtain styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon), adopt methods such as steam distillation thoroughly to remove pore-foaming agent again.
The present invention at chemical formula and the optimum formula by weight that the two nets of secondary pass through 2～4 kinds of function monomers, diluent and crosslinking agents used in the crosslinking copolymerization course of reaction mutually is:
Function monomer CH
2=CR
1R
210～30 parts
Inert diluent C
nH
mAnd C
qH
pCOOR
310～20 parts of equivalent proportionings
Crosslinking agent CH
2=CHR
4CH=CH
21～3 part
N, m, q and p are 2～10 positive integer in the formula, R
1, R
2Can be H, CH
3, COOC
nH
m, COOH, CN and C
6H
5Deng, R
3Can be C
nH
m, R
4Can be C
6H
4, CONH-CH
2-HNCO or COOC
2H
4OOC etc.
Carry out the two nets of secondary according to optimum formula and the conventional suspension polymerisation condition of reference and pass through the crosslinking copolymerization reaction mutually, promptly obtain macroporous adsorption resin special used for separating antibiotic with hot water or cold water's cyclic washing again.
2, specific embodiment:
Synthesizing of styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon)
In the 1000ml there-necked flask, add distilled water 400ml and gelatin 6g, stir and be heated to 60 ℃ it is dissolved fully.Add simultaneously styrene 10ml, divinylbenzene 80ml, pore-foaming agent toluene 120ml and initator dibenzoyl peroxide (BPO) 2g in the 500ml conical flask successively, stirring is dissolved it fully.The latter is added there-necked flask, the control stirring intensity makes the monomer droplet particle diameter in the 0.3-1.0mm scope, temperature programming to 80 ℃ reaction 4h, be warming up to 100 ℃ of reaction 4h again, hot wash, adopt steam distillation to remove pore-foaming agent at last, promptly obtain styrene-divinylbenzene macropore copolymerization bead intermediate (St-DVB Archon).
3, specific embodiment:
The two nets of antibiotic separate, dedicated secondary pass through the synthetic of cross-linked adsorbing resin mutually
In the 1000ml there-necked flask, add distilled water 200ml, styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) 200g and stabilizing agent 30g successively, in the 250ml conical flask, add simultaneously function monomer such as acrylonitrile 10ml, butyl methacrylate 10ml, crosslinking agent divinylbenzene 2ml and diluent butyl acetate 10ml successively, the vibration dissolving, it is added in the there-necked flask, stir 2-4h at ambient temperature and make the full and uniform Archon inside that diffuses into of function monomer solution.Temperature programming to 80 ℃ reaction 4h is warming up to 100 ℃ of reaction 4h again, and hot wash promptly obtains the two nets of antibiotic separate, dedicated secondary and passes through cross-linked adsorbing resin mutually.
4, effect embodiment (1):
From streptomyces erythreus fermentation cleaner liquid, separate erythromycin and crystallization thereof
The two nets of filling secondary pass through cross-linked adsorbing resin 450ml mutually in φ 40 * 500mm glass adsorption column, the tire streptomyces erythreus fermentation cleaner liquid of concentration 2000-5000u/ml of control erythromycin flows through adsorption column with the flow velocity from top to down of 17-50ml/min, then wherein the erythromycin more than 99% flows out liquid erythromycin concentration＜50u/ml promptly by resin adsorption.When detecting erythromycin and leak concentration＞100u/ml, series connection inserts second adsorption column.
Detect first post and reach absorption when saturated, add distilled water drip washing to clean residual zymotic fluid in the post, add acetone 450ml again, control its flow velocity from top to down and flow through adsorption column with 10-20ml/min, Fractional Collections flows out liquid, is respectively applied for crystallization erythromycin and cover and is used for next desorb.
Under stirring condition, in tiring the leading portion stripping liquid of concentration 120-160ku/ml, erythromycin adds distilled water according to 2: 1 ratios, 35 ℃＞8h of insulation, filter the erythromycin crystal, 100 ℃ of oven dry, it is dissolved in acetone and be recrystallized according to same process, filter and the oven dry crystal, promptly reached the erythromycin crystallization of 1995 editions " Pharmacopoeia of People's Republic of China standards " comprehensively.
5, effect embodiment (2):
Separate recovery erythromycin and acetone respectively from the acetone crystalline mother solution of butyl acetate extraction process
In the erythromycin production procedure of existing butyl acetate extraction-lactate crystallization-acetone solution-commentaries on classics alkali crystallization, the erythromycin concentration of the acetone crystalline mother solution that is produced (being commonly called as third mother liquor) is about 3000u/ml, acetone concentration about 30%, current technology directly adopts rectification process only to reclaim wherein acetone, and do not consider that wherein the separation of erythromycin is reclaimed, thereby cause the waste of precious resources.
The two nets of filling secondary pass through cross-linked adsorbing resin 450ml mutually in φ 40 * 500mm glass adsorption column, the control erythromycin concentration is about 3000u/ml, the crystalline mother solution of acetone concentration about 30% flows through adsorption column with the flow velocity from top to down of 10-20ml/min, then surpasses 95% erythromycin in the mother liquor and is lower than 5% acetone promptly by resin adsorption.Reach absorption saturated after, adopt the acetone desorb with reference to effect embodiment (1), add the distilled water diluting stripping liquid according to 2: 1 ratio again, through leaving standstill and flow process such as crystallization, can obtain the erythromycin crystal.Crystalline mother solution after resin adsorption adopts rectification process to reclaim acetone again.
Claims (2)
1, a kind of macroporous adsorption resin special used for separating antibiotic, it is characterized in that: with styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) is raw material, adopt 2～4 kinds of function monomers and crosslinking agent, under the condition that peroxide initiator, water and inorganic salts exist, carrying out the two nets of secondary, to pass through the crosslinking copolymerization reaction mutually synthetic; The prescription of described styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) is by weight:
5～20 parts of styrene (St)
80～100 parts of 80% divinylbenzenes (DVB)
0.5～2.5 part of dibenzoyl peroxide (BPO)
50～150 parts of pore-foaming agents (toluene, atoleine and gasoline one)
1～5 part in gelatin
300～600 parts of distilled water
The chemical formula of described crosslinking agent is: CH
2=CHR
4CH=CH
2
2, the preparation method of macroporous adsorption resin special used for separating antibiotic is characterized in that following steps:
(1), carry out conventional suspension polymerization according to the prescription of above-mentioned styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) and promptly obtain styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon), adopt steam distillation to remove pore-foaming agent again;
(2), the styrene-divinylbenzene macropore copolymerization bead (St-DVB Archon) that obtains carried out the two nets of secondary pass through the crosslinking copolymerization reaction mutually, the prescription that the two nets of secondary pass through the crosslinking copolymerization reaction mutually is by weight:
50～100 parts of St-DVB Archons
Totally 5～50 parts of 2～4 kinds of function monomers
0.5～5 part of peroxide initiator
10～50 parts of inert diluents
5～20 parts of stabilizing agents
100～300 parts of distilled water
Pass through the prescription of crosslinking copolymerization reaction mutually according to the two nets of secondary, adopt conventional suspension polymerization to carry out the two nets of secondary and pass through the crosslinking copolymerization reaction mutually, promptly obtain macroporous adsorption resin special used for separating antibiotic with hot water or cold water's cyclic washing again.
The chemical formula of described 2～4 kinds of function monomers is: CH
2=CR
1R
2
Described inert diluent is: chemical formula C
nH
mAnd C
qH
pCOOR
3The material equal proportion mix
N, m, q and p are 2～10 positive integer in the formula, R
1, R
2Be H, CH
3, COOC
nH
m, COOH, CN or C
6H
5, R
3Be C
nH
m, R
4Be C
6H
4, CONH-CH
2-HNCO or COOC
2H
4OOC.
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|---|---|---|---|
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| CN100467120C CN100467120C (en) | 2009-03-11 |
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| CN101693750B (en) * | 2009-10-16 | 2011-09-07 | 崔建 | Preparation method of macroporous absorption resin |
| CN102178003A (en) * | 2011-03-30 | 2011-09-14 | 浙江永金茶业有限公司 | Process for extracting tea polyphenol |
| CN102294230A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula of ultrahigh cross-linked styrene macroporous adsorbent and process route thereof |
| CN102294228A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula of ultrahigh cross-linked styrene macroporous adsorbent and process route thereof |
| CN102295724A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula for hypercrosslinked styrene macroporous adsorbent and process route thereof |
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| CN107445242A (en) * | 2017-09-13 | 2017-12-08 | 大连理工大学 | A kind of adsorbed film that Multiple Classes of Antibiotics is synchronously fixed under sea conditions |
| CN108164622A (en) * | 2018-02-28 | 2018-06-15 | 江苏苏青水处理工程集团有限公司 | A kind of preparation method of Thermal Stable Anion Exchange Resin |
| CN109553650A (en) * | 2017-09-25 | 2019-04-02 | 联邦制药(内蒙古)有限公司 | The aqueous extraction method of erythromycin fermentation liquid |
| CN114437275A (en) * | 2020-11-05 | 2022-05-06 | 万华化学集团股份有限公司 | High-specific-surface-area adsorption resin and application thereof in removing dinotefuran residues |
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| CN101693750B (en) * | 2009-10-16 | 2011-09-07 | 崔建 | Preparation method of macroporous absorption resin |
| CN102294230A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula of ultrahigh cross-linked styrene macroporous adsorbent and process route thereof |
| CN102294228A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula of ultrahigh cross-linked styrene macroporous adsorbent and process route thereof |
| CN102295724A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula for hypercrosslinked styrene macroporous adsorbent and process route thereof |
| CN102178003A (en) * | 2011-03-30 | 2011-09-14 | 浙江永金茶业有限公司 | Process for extracting tea polyphenol |
| CN104497193A (en) * | 2014-10-01 | 2015-04-08 | 于杰 | Active vector for removing in vivo toxic substance including endotoxin in intestinal tracts |
| CN104525149A (en) * | 2014-11-10 | 2015-04-22 | 苏州维泰生物技术有限公司 | Middle molecule adsorbent for epidemic hemorrhagic fever and preparation method thereof |
| CN104525149B (en) * | 2014-11-10 | 2016-11-02 | 浙江康诚工业产品设计有限公司 | Middle molecule adsorbent for epidemic hemorrhagic fever and preparation method thereof |
| CN107118303A (en) * | 2017-05-31 | 2017-09-01 | 环境保护部南京环境科学研究所 | A kind of preparation and application of modified wheat stalk cellulose |
| CN107445242A (en) * | 2017-09-13 | 2017-12-08 | 大连理工大学 | A kind of adsorbed film that Multiple Classes of Antibiotics is synchronously fixed under sea conditions |
| CN107445242B (en) * | 2017-09-13 | 2020-08-14 | 大连理工大学 | Adsorption film for synchronously fixing multiple antibiotics under seawater condition |
| CN109553650A (en) * | 2017-09-25 | 2019-04-02 | 联邦制药(内蒙古)有限公司 | The aqueous extraction method of erythromycin fermentation liquid |
| CN109553650B (en) * | 2017-09-25 | 2020-11-20 | 联邦制药(内蒙古)有限公司 | Water phase extraction method of erythromycin fermentation liquor |
| CN108164622A (en) * | 2018-02-28 | 2018-06-15 | 江苏苏青水处理工程集团有限公司 | A kind of preparation method of Thermal Stable Anion Exchange Resin |
| CN114437275A (en) * | 2020-11-05 | 2022-05-06 | 万华化学集团股份有限公司 | High-specific-surface-area adsorption resin and application thereof in removing dinotefuran residues |
| CN114437275B (en) * | 2020-11-05 | 2023-10-20 | 万华化学集团股份有限公司 | High specific surface area adsorption resin and application thereof in removing dinotefuran residues |
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