CN1257925C - (ABC) S type asteroid polymer in hetero arm and preparation method - Google Patents
(ABC) S type asteroid polymer in hetero arm and preparation method Download PDFInfo
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- CN1257925C CN1257925C CN 200410017531 CN200410017531A CN1257925C CN 1257925 C CN1257925 C CN 1257925C CN 200410017531 CN200410017531 CN 200410017531 CN 200410017531 A CN200410017531 A CN 200410017531A CN 1257925 C CN1257925 C CN 1257925C
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Abstract
The present invention relates to a new method of preparing ABC type asteroid polymers with hetero arms. The present invention and the preparing method are completely different from the existing product and a synthesis method. The present invention is an asteroid polymer with unequal arms. The synthesis method uses a coupled reaction of the field of biochemistry, and connects macromolecule homopolymers with terminal groups with different functional groups of amino acid or the derivative of the amino acid one by one. The method can be used for synthesizing ABC type asteroid polymers with hetero arms with all kinds of combination. The present invention has the advantages of mild reaction condition and easy industrialized production.
Description
Technical field
The present invention is the method for the assorted arm star polymer of a kind of preparation (ABC) S type.
Background technology
The molecular designing of ad hoc structure and synthetic scientific research still aspect the industrial application all highly significant, become the research theme that becomes increasingly active.Synthesize radial copolymer different by structure and that each inconsistent component is formed, on the one hand they can provide the novel material of various performance optimizations combinations on higher level for modern technologies, multiple use can be arranged, comprise polymeric surface active agent, the expanding material of destaticizer, polymer blended usefulness, phase-transfer catalyst or solid polymer electrolyte etc.These new new phase morphologies that radial copolymer had on the other hand, phase structure, phase interface and phase size, these new facies relationships are with the variation of the structure and the length of each chain, and their macroscopical physics and information such as chemical property and aggregated structure thereof, all be the very interested research topic of polymer science worker.At present, according to the literature, active anion, positively charged ion and radical polymerization can be used for synthesizing star polymer, and the star polymer of above polymerization process preparation is with comparatively common with arm configuration, and the assorted arm polymkeric substance of preparation often is confined to be fit to a few monomeric combination of certain polymerization mechanism.Certainly, the people is also arranged the different polymerization mechanism synthetic star polymer that combines, but the aforesaid method severe reaction conditions is difficult to industrialization, does not have universality.
Summary of the invention
The objective of the invention is to obtain the assorted arm star polymer of a kind of broad-spectrum (ABC) S type.
The objective of the invention is to obtain a kind of preparation method of the assorted arm star polymer of (ABC) S type of easy and simple to handle, easy industrialization.
The present invention utilizes the terminal group of the polymkeric substance of functional end-groupization to prepare the assorted arm star polymer of (ABC) S type with being with multi-functional Methionin and derivative generation coupled reaction thereof.The living polymerization of energy functionalization comprises anionoid polymerization, cationoid polymerisation, and therefore active free radical polymerization is applicable to that homopolymer scope of the present invention is wider.And Methionin is of a great variety, and obtains easily.
The general formula of target product of the present invention is:
Be designated as: (ABC) S
A, B, C are the polymer homopolymer that end contains functional group, and functional group etc. can be amido, hydroxyl, carboxyl, maleimide etc.A, B, C can be variant, the segregative homopolymer of character such as polystyrene, polyisoprene, polyoxyethylene glycol, poly 4 vinyl pyridine, polyhutadiene, polyacrylate(s), and number-average molecular weight is between 2000-20000.S is the Methionin or derivatives thereof that three functional groups are arranged.
S of the present invention can be the Methionin or derivatives thereof, and such origin of amino acid is extensive, and reaction is convenient.
S of the present invention can also be the derivative of Methionin, as has dipeptides, tripeptides of three functional groups etc.
The assorted arm star polymer of above-mentioned (ABC) S type is the type homopolymer by one or both ends band functional group, with the functional group of Methionin one by one coupling obtain.The functional group of homopolymer can be amido, carboxyl, hydroxyl, maleimide etc.
The homopolymer of hydroxy functional group must be after being converted into functional group of Acibenzolar functional group and the coupling of Methionin or derivatives thereof.Polymkeric substance there is not particular requirement, as long as can separation and purification under existing separation means.
The solvent that the present invention uses in building-up process should be the common good solvent of the polymer homopolymer of participating in reaction, and intermediate product and final product can be purified with the chromatography chromatographic column; The molecular weight of product and molecular weight distribution can be used gel permeation chromatography, and each component concentration can be used nuclear magnetic resonance spectroscopy in the product.
The concrete steps of the coupled reaction that the present invention adopts are the biochemical reaction of prior art, reaction conditions gentleness, easy to control, and these those skilled in the art all can realize by foregoing of the present invention, obtain target product.
The present invention can make the polymkeric substance of ASB two blocks earlier, i.e. preparation homopolymer A and Methionin or derivative coupling earlier, and then with homopolymer B coupling, last and two ends are all with the arbitrary end of the homopolymer C of functional group and the S coupling on the ASB, make the assorted arm star polymer of (ABC) S type of band edge base on the C chain, this base polymer can also be connected on other polymkeric substance with functional group.
The inventive method judges by end group analysis whether each stage coupled reaction is complete, promptly carries out the coupled reaction of next homopolymer and Methionin or derivative after fully again when coupled reaction each time.
The present invention has widened the preparation approach of this base polymer, and the preparation method is easy, general, and the reaction conditions gentleness has good industrial prospect.
Embodiment
Embodiment one
(PSPEGPI) preparation of lysine
The preparation flow signal
One, the preparation of MPEG-lysine
1, the preparation of mPEG-O-NHS
With 10gmPEG-OH (Mn=2783,3.59mmol) be dissolved in the 200ml toluene, evaporate to dryness toluene behind the azeotropic water removing, add acetonitrile 100ml while hot, add triethylamine 6ml (43mmol), add two succinimdyl carbonates (DSC) 5.5g (21.5mmol) and acetonitrile 50ml in another flask, the dissolving back drips the second eyeball solution of back, stirring reaction 12h under room temperature.
Reaction solution with the anhydrous diethyl ether precipitation, is dissolved in 50ml toluene again after concentrating, filter, and removes insoluble DSC.In the exsiccant anhydrous diethyl ether, be settled out again, and in methylene dichloride/ether twice of dissolution precipitation.Vacuum-drying gets MPEG-O-NHS9.0g, productive rate 90%
Measure the content of mPEG-O-NHS: mPEG-O-NHS is dissolved in the buffered soln of PH=9, and (concentration is 0.5-1.0 * 10
-4Mol/L places 30min, measures its ultraviolet light absorption spectrum.The absorbancy at record 260nm place, and by mole extinction coefficient epsilon=8900 (mol/L)
-1Cm
-1Calculate the wherein content of Acibenzolar.
2, the preparation of MPEG-lysine
Take by weighing 4.72g (32mmol) Methionin, be dissolved in the buffered soln of 150ml pH=8, regulate pH 8.30, add exsiccant mPEG-O-NHS 9g altogether in batches with rare HCl solution, regulate pH between 8.30 to 8.00 with dilute NaOH solution in this process, reaction is spent the night.
Regulate PH=3.0 with dilute hydrochloric acid, use dichloromethane extraction 5 times.Concentrate precipitation.Vacuum-drying gets MPEG-lysine8.3g, productive rate 92%.
Two, the preparation of PSPEG-lysine
1, the preparation of PS-O-NHS
(Mn=4319 1.157mmol) is dissolved in the 100ml toluene, and evaporate to dryness toluene behind the azeotropic water removing adds purified methylene dichloride 30ml, adds 4-Dimethylamino pyridine (DMAP) 0.846g (6.942mmol) with 5g PS-OH.
Add 1.782gDSC (6.942mmol) and purified acetone 90ml in another flask, the dichloromethane solution that the dissolving back drips back reacts spend the night (greater than 12 hours).
With reaction solution evaporate to dryness at low temperatures, be dissolved in toluene again, filter, remove insoluble DSC.After being spin-dried for toluene, pour hexanaphthene 100ml into, filter, remove insolubles, be spin-dried for again,, get PS-O-NHS4.2g, productive rate 84% with three times final vacuum dryings of exsiccant second eyeball washing.
2, the preparation of PSPEG-lysine
(Mn=2783 0.72mmol) adds exsiccant chloroform 80ml, adds triethylamine and regulates PH between 9 to 10 to take by weighing 2gMPEG-lysine.(Mn=4319 0.9mmol) is added dropwise to this solution with 4g PS-O-NHS.Reaction is 3 hours under the room temperature, and oil bath is heated to 50 ℃ then, reacts 3 days, takes out on a small quantity, is settled out in sherwood oil (30 ℃-60 ℃), with dehydrated alcohol flush away triethylamine.Detect by amino then and judge whether that MPEG-lysine exists in addition.If also have, add an amount of PS-O-NHS.Until there not being amino the existence.Be spin-dried for reaction solution, in sherwood oil (30 ℃-60 ℃), be settled out, with anhydrous methanol flush away triethylamine.
By the separation and purification of chromatography chromatographic column, go out PS with eluent methylene chloride earlier, use methylene chloride drip washing (9: 1) again, with ultraviolet, infrared detection leacheate, be spin-dried for required component leacheate, in sherwood oil, be settled out, vacuum-drying gets PSPEG-lysine 3g, productive rate 60%.Measure Mn=6109 with GPC, D=1.12 (PS is as standard specimen).
Three, the preparation of PSPEGPI-lysine
1, PI-NH
2Preparation
1) preparation of PI-O-NHS
(Mn=3472,0.864mmol), the preparation method is identical with PS-O-NHS's to get 3g PI-OH.
2) PI-NH
2Preparation
Get quadrol 1.155ml (17.3mmol), add an amount of methylene dichloride 60ml, slowly drip the dichloromethane solution of PI-O-NHS, reaction is spent the night.After being spin-dried for methylene dichloride, in methyl alcohol, be settled out, repeatedly with methanol wash to remove quadrol, up to twice detected amido content difference less than 2%, vacuum-drying, 2.5g, productive rate 83%.
2, the preparation of PSPEGPI-lysine
1) preparation of PSPEG-lysine-COO-NHS
Take by weighing PSPEG-lysine 1.0g (0.141mmol), methylbenzene azeotropic dewaters, add trichloromethane 20ml dissolving, add N-hydroxy-succinamide 0.065g (0.423mmol), after waiting to dissolve, under the ice-water bath, drip N, reaction is after 1 hour down for the chloroform soln of N '-dicyclohexylcarbodiimide 0.145g (0.564mmol), ice-water bath, and normal temperature reaction down spends the night.Reacted after-filtration to remove N, N '-dicyclohexylurea (DCU) preserves the filtrate sealing.
2) take by weighing PI-NH
21.5g (0.423mmol) be dissolved in the chloroform soln, add triethylamine, regulate pH value between 9-10, drip the filtrate of previous step, after dropwising, oil bath 40 degree reacted 14-21 days.Concentration of reaction solution, by the separation and purification of chromatography chromatographic column, earlier go out PI with eluent methylene chloride, use methylene chloride drip washing (9: 1) again,, be spin-dried for required component leacheate with ultraviolet, infrared detection leacheate, in sherwood oil, be settled out, vacuum-drying gets PSPEGPI-lysine 1g, productive rate 70%.Measure Mn=9294 with GPC, D=1.08 (PS is as standard specimen).
Embodiment two
NH
2The preparation of one (PSPEGPI) lysine
The preparation flow signal
One, the preparation of PS-lysine-COOH (2)
1) preparation of PS-ONHS (the same)
2) PS-lysine-COOC
2H
5Preparation
Add the exsiccant chloroform in there-necked flask, add ethyl ester of lysine hydrochloride (molar weight of PS * 5 * 248), add triethylamine 5ml, logical nitrogen after waiting to dissolve, drips the chloroformic solution of PS-ONHS, and reaction is 3 hours under the room temperature, oil bath 40 degree reactions 24 hours.Chloroform is spin-dried for, adds the toluene dissolving, remove by filter insolubles, concentrate toluene solution, in methyl alcohol, be settled out, suction filtration, 35 degree vacuum dryings.
3) preparation of PS-lysine-COOH
With 5g PS-lysine-COOC
2H
5Be dissolved in the 25ml tetrahydrofuran (THF), stir the aqueous solution 5ml (3mol/L) that adds NaOH down, reaction is spent the night under the room temperature, with dilute hydrochloric acid solution is transferred to neutrality, is spin-dried for THF, is deposited in the methyl alcohol oven dry.
Two, the preparation of PSPI-lysine-COOH
1) preparation of PI-O-NHS (carbamate)
Identical with the preparation of PS-O-NHS (carbamate)
2) preparation of PSPI-lysine-COOH
Take by weighing a certain amount of PS-lysine (control PI-O-NHS is 1.25 to 1.5 times of PS-lysine consumption), add exsiccant chloroform (chloroform), add triethylamine and regulate PH between 9 to 10.PI-O-NHS is added dropwise to this solution.Reaction is 3 hours under the room temperature, heats then oil bath 3-7 days, takes out on a small quantity, is settled out in methyl alcohol, with methyl alcohol flush away triethylamine.Detect by amino then and judge whether that PS-lysine exists in addition.If also have, add an amount of PI-O-NHS.Until there not being amino the existence.Be spin-dried for reaction solution, be settled out in methyl alcohol, with methyl alcohol flush away triethylamine, vacuum-drying is measured with GPC.
Three, NH
2The preparation of-PEGPSPI-lysine
Take by weighing the thick product of a certain amount of PSPI-lysine-COOH, methylbenzene azeotropic dewaters, add the trichloromethane dissolving, add HOSu (molar weight of PSlysine * 5 * 115), after waiting to dissolve, under the ice-water bath, drip the chloroform soln of DCC (molar weight of PS-lysine * 6 * 206), react after 1 hour, normal temperature reaction down spends the night.Reacted after-filtration to remove DCU, the filtrate sealing has been preserved.
Take by weighing a certain amount of NH
2-PEG-NH
2, (be PS-lysine consumption 3 times) is dissolved in the chloroform soln, adds triethylamine, regulates pH value between 9-10, drips the filtrate of previous step, and after dropwising, oil bath 40 degree reacted 14-21 days.Concentration of reaction solution by the separation and purification of chromatography chromatographic column, goes out PS with eluent methylene chloride, PI earlier, and PSPI-lysine, use methylene chloride drip washing (9: 1) again, with ultraviolet, infrared detection leacheate, be spin-dried for required component leacheate, in sherwood oil, be settled out vacuum-drying.
Embodiment three
(PSPEGPI) (lysine)
2Preparation
One, PSPEG-(lysine)
2Preparation
In there-necked flask, add exsiccant DMF, add ethyl ester of lysine hydrochloride (molar weight of PSPEG-lysine-COO-NHS * 5 * 248), add triethylamine 5ml, logical nitrogen, after waiting to dissolve, drip the chloroformic solution (preparation method is the same) of PSPEG-lysine-COO-NHS, reaction is 3 hours under the room temperature, oil bath 40 degree reactions 48 hours.Chloroform is spin-dried for, adds the toluene dissolving, remove by filter insolubles, concentrate toluene solution, in sherwood oil, be settled out, suction filtration, 35 degree vacuum dryings.
With PSPEG-(lysine)
2-COOC
2H
5Be dissolved in the 25ml tetrahydrofuran (THF), stir the aqueous solution 5ml (3mol/L) that adds NaOH down, reaction is spent the night under the room temperature, with dilute hydrochloric acid solution is transferred to subacidity, be spin-dried for THF, be deposited in the sherwood oil, with methanol wash repeatedly, vacuum-drying obtains PSPEG-(lysine)
2
Two, PSPEGPI-(lysine)
2Preparation
Take by weighing a certain amount of PSPEG-(lysine)
2, add exsiccant chloroform (chloroform), add triethylamine and regulate PH between 9 to 10.PI-O-NHS is added dropwise to this solution.Reaction is 3 hours under the room temperature, heats then oil bath 7-14 days, takes out on a small quantity, is settled out in methyl alcohol, with methyl alcohol flush away triethylamine.Detect by amino then and judge whether PSPEG-(lysine) in addition
2Exist.If also have, add an amount of PI-O-NHS.Until there not being amino the existence.Concentration of reaction solution by the separation and purification of chromatography chromatographic column, goes out PS with eluent methylene chloride, PI earlier, and PSPI-lysine, use methylene chloride drip washing (9: 1) again, with ultraviolet, infrared detection leacheate, be spin-dried for required component leacheate, in sherwood oil, be settled out vacuum-drying.
Above-mentioned each abbreviation is expressed as follows:
(PSPEGPI) lysine is to be centronucleus with Methionin, and polystyrene, polyoxyethylene glycol, polyisoprene are the assorted arm segmented copolymer of arm.
MPEG-lysine is the mono methoxy polyethylene glycol that end connects Methionin.
MPEG-OH is the terminal mono methoxy polyethylene glycol of hydroxyl that is.
MPEG-O-NHS is the terminal mono methoxy polyethylene glycol of succinimdyl carbonate that is.
PSPEG-lysine is to be centronucleus with Methionin, and polystyrene, polyoxyethylene glycol are received two segmented copolymers that amino obtains of Methionin respectively.
PS-O-NHS is the terminal polystyrene of succinimdyl carbonate that is.
PS-OH is the terminal polystyrene of hydroxyl that is.
DSC is two succinimdyl carbonates.
DMAP is the 4-Dimethylamino pyridine.
PI-NH
2It is the terminal polyisoprene of amido that is.
PI-O-NHS is the terminal polyisoprene of carbonic ether that is.
PSPEG-lysine-COO-NHS is converted into the succinimide carboxylicesters with centronucleus Methionin.
NH
2-(PSPEGPI) lysine is to be centronucleus with Methionin, polystyrene, polyoxyethylene glycol, polyisoprene are the assorted arm segmented copolymer of arm, have an amido at an end of polyoxyethylene glycol.
PS-lysine-COOC
2H
5It is the polystyrene that end connects ethyl ester of lysine.
PS-lysine-COOH is the polystyrene that end connects Methionin.
PSPI-lysine-COOH is to be centronucleus with Methionin, and polystyrene, polyisoprene are received the segmented copolymer that obtains on two amino of Methionin respectively.
HOSu is a N-hydroxy-succinamide.
DCC is N, N '-dicyclohexylcarbodiimide.
DCU is N, N '-dicyclohexylurea (DCU).
NH
2-PEG-NH
2Be that two ends are the polyoxyethylene glycol of amido.
(PSPEGPI) (lysine) 2 be that the dipeptides that forms with two Methionins is a centronucleus, polystyrene, polyoxyethylene glycol, polyisoprene are the assorted arm segmented copolymer of arm.
PSPEG-(lysine)
2Be that the dipeptides that forms with two Methionins is a centronucleus, polystyrene, polyoxyethylene glycol are received the segmented copolymer that obtains on two amino of Methionin respectively.
PSPEG-(lysine)
2-COOC
2H
5Be that the dipeptides that forms with two Methionins is a centronucleus, one of them Methionin exists with the form of ethyl ester of lysine, and polystyrene, polyoxyethylene glycol are received the segmented copolymer that obtains on two amino of Methionin respectively.
Claims (5)
1 one kinds of assorted arm star polymers of (ABC) S type is characterized in that chemical structure is as follows:
Wherein A, B, C are that end has amido or hydroxyl or carboxyl, or the polymer homopolymer of maleimide amine functional group, and S is the Methionin or derivatives thereof that three functional groups are arranged, and the number-average molecular weight of homopolymer is between 2000-20000.
The method of the assorted arm star polymkeric substance of 2 preparation according to claim 1 (ABC) S types is characterized in that S is the derivative that three functional group's Methionins are arranged, and this derivative is the peptide that three functional groups are arranged.
The preparation method of the assorted arm star polymer of 3 (ABC) according to claim 1 S type, it is characterized in that to contain the polymer homopolymer and Methionin or derivatives thereof coupling one by one of functional group with three functional groups, separation and purification promptly gets product, wherein hydroxy functional groups get homopolymer must be after being converted into Acibenzolar functional group and the coupling of Methionin or derivatives thereof.
The preparation method of the assorted arm star polymer of 4 (ABC) according to claim 1 S type, it is characterized in that making earlier two blocks and get ASB, then by two ends all with the arbitrary end of the homopolymer C of functional group and the S coupling on the ASB, make the assorted arm star polymer of (ABC) S type of band edge base on the C chain.
The preparation method of the assorted arm star polymer of 5 (ABC) according to claim 1 S type is characterized in that judging level of response by end group analysis.
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| CN 200410017531 CN1257925C (en) | 2004-04-07 | 2004-04-07 | (ABC) S type asteroid polymer in hetero arm and preparation method |
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| CN 200410017531 CN1257925C (en) | 2004-04-07 | 2004-04-07 | (ABC) S type asteroid polymer in hetero arm and preparation method |
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| CN1257925C true CN1257925C (en) | 2006-05-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870767B (en) * | 2009-04-24 | 2012-09-12 | 石药集团中奇制药技术（石家庄）有限公司 | Preparation method of pegylated 1,2-bialiphatic acyl phosphatidylethanolamine |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143916B (en) * | 2007-08-30 | 2010-11-17 | 复旦大学 | Method for preparing three hetero arms asteroid polymer |
| CN103194123A (en) * | 2012-01-06 | 2013-07-10 | 任天斌 | Aqueous nano-paste and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101870767B (en) * | 2009-04-24 | 2012-09-12 | 石药集团中奇制药技术（石家庄）有限公司 | Preparation method of pegylated 1,2-bialiphatic acyl phosphatidylethanolamine |
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