CN105801457A - Terminal alkynyl containing RAFT chain transfer agent and preparation method and application thereof - Google Patents
Terminal alkynyl containing RAFT chain transfer agent and preparation method and application thereof Download PDFInfo
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- CN105801457A CN105801457A CN201610192582.7A CN201610192582A CN105801457A CN 105801457 A CN105801457 A CN 105801457A CN 201610192582 A CN201610192582 A CN 201610192582A CN 105801457 A CN105801457 A CN 105801457A
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- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
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Abstract
The invention belongs to the field of organic synthesis and discloses a terminal alkynyl containing RAFT chain transfer agent and a preparation method and application thereof.The RAFT chain transfer agent has a structure shown in the description.The preparation method comprises the steps that tert-butyl mercaptan serves as a start raw material and reacts with carbon disulfide under the action of alkali to form trithiocarbonate; under the alkaline catalytic action, the obtained trithiocarbonate reacts with bromo propionate, and after acidification, terminal carboxylgroup containing RAFT chain transfer agent is obtained; the terminal carboxylgroup containing RAFT chain transfer agent is re-crystalized through n-hexane, and then under the action of EDC.HC1 and DMAP, the terminal carboxylgroup containing RAFT chain transfer agent and propargyl alcohol generate terminal alkynyl containing trithiocarbonate.The rough product is subjected to extraction and column chromatography, and then the product is obtained.The terminal alkynyl containing RAFT chain transfer agent can achieve RAFT polymerization and click reaction and prepare block polymer with specific structures and functions.
Description
Technical field
The invention belongs to organic synthesis field, particularly to a kind of reversible addition-fracture chain containing terminal acetylene functional group
Transferring free-radical polymerization chain transfer agents (RAFT reagent) and its preparation method and application.
Background technology
After RAFT active free radical polymerization mechanism proposes, researcher starts to put into the research to RAFT reagent
Work.The RAFT reagent reported at present, by the difference of its structure, mainly has: (1) dithioesters, (2) trithiocarbonate,
(3) dithiocarbonates, (4) dithiocarbamate.The active center that RAFT agent (CTA) is polymerized as RAF, it
Structure directly influence RAFT polymerization polymerization process, the molecular weight dispersity of polymer, and different types of free radical
Monomer is also applied for the RAFT agent of different structure.
In recent years, RAFT polymerization has developed into the polymerization means of a kind of routine, is usually combined with other polymerizations
Synthesize a series of polymerization ad hoc structure and the polymer of function.Patent CN 103819390 A discloses a kind of containing terminal hydroxyl
RAFT reagent, terminal hydroxyl is active group, and RAFT polymerization can combine preparation one fixed structure with ring-opening polymerisation (ROP)
Block copolymer；Patent CN 104592072 A discloses a kind of RAFT agent containing terminal carboxyl group, after RAFT polymerization
Polymer is further modified by the carboxyl that this chain-transferring agent end can be utilized to contain.
Click chemistry (click chemistry) is by the calendar year 2001 Americanized scholar of Nobel chemistry Prize winner
Sharpless proposes first.A topmost class click chemistry reaction is Cu (I) compound for catalysis azido compound and alkynyl
Compound reaction generates 1,2,3-triazoles 5-membered ring compounds, and two kinds of different materials can be risen by it by five-membered ring covalent bond
Come.It is excellent that the method possesses that yield is high, efficiency high, side reaction is few, reaction condition is gentle, separating-purifying is simple, environmental pollution is little etc.
Point, is therefore widely used.
Will click on chemical combining with RAFT polymerization and can prepare the macromolecule polyalcohol with certain 26S Proteasome Structure and Function, and
Realize that click chemistry is polymerized with RAFT it is critical that whether RAFT agent end contains the base that can participate in click-reaction
Group's (such as end alkynyl radical, azido group).Therefore design the RAFT agent containing corresponding construction become and will click on chemistry
It is polymerized combination with RAFT, prepares the key link of ad hoc structure polymer.
At present, most RAFT agent does not has band and can participate in the group of click-reaction, it is impossible to utilizes and clicks on
Chemistry modification further to polymer, thus click chemistry cannot be directly applied to and be polymerized combination with RAFT, preparation has specific
26S Proteasome Structure and Function polymer.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of containing terminal acetylene
RAFT agent.
Another object of the present invention is to provide the preparation method of the above-mentioned RAFT agent containing terminal acetylene.
It is still another object of the present invention to provide the application of the above-mentioned RAFT agent containing terminal acetylene.
The purpose of the present invention is achieved through the following technical solutions:
A kind of RAFT agent containing terminal acetylene, this RAFT agent has a structure being shown below:
Named: the S-tert-butyl group-S ,-isopropyl acid propine ester group trithiocarbonate.
The preparation method of the above-mentioned RAFT agent containing terminal acetylene, comprises the steps: that (1) with tert-butyl mercaptan is
Initiation material, under the effect of alkali generate mercaptides, then with Carbon bisulfide effect, generate trithiocarbonate；Gained trithio
Carbonate reacts with 2 bromopropionic acid under the catalytic action of alkali, obtains the RAFT agent containing terminal carboxyl group after acidifying；
(2) by the RAFT agent containing terminal carboxyl group of (1) gained after normal hexane recrystallization, 1-(3-dimethylamino-propyl)-
Generate with propargyl alcohol esterification under 3-ethyl-carbodiimide hydrochloride (EDC HCl) and the effect of DMAP (DMAP)
A kind of trithiocarbonate containing terminal acetylene, by crude product by experimental techniques such as extraction, column chromatographies, finally gives containing end
The RAFT agent of alkynyl.
The preparation method of the above-mentioned RAFT agent containing terminal acetylene, specifically includes following steps:
(1) sodium hydroxide solution 1 is dropped to the mixed solution of tert-butyl mercaptan and the distilled water 1 being under stirring
In, generate mercaptides；Then drip acetone, obtain colourless transparent solution, then drip the body that Carbon bisulfide cools down to ice bath
System obtains orange solution；After stirring, then dripping 2 bromopropionic acid in system, then dropping sodium hydroxide solution 2, treats that temperature is steady
Fixed, add distilled water 2 and be diluted；After reaction overnight is stirred at room temperature；In system, add distilled water 3 dilute, lower of condition of ice bath
Adding concentrated hydrochloric acid makes system be acidity and stir, and yellow oil occurs, continues stirring until grease becomes solid-state；After sucking filtration, use
Cold distilled water constantly rinses, and dried and recrystallization must contain the RAFT agent of terminal carboxyl group；
(2) by the RAFT agent containing terminal carboxyl group of step (1) gained and 1-(3-dimethylamino-propyl)-3-ethyl
Carbodiimide hydrochloride (EDC HCl) dissolves with DMAP (DMAP) dichloromethane, is stirred continuously and blasts argon
Gas, propilolic alcohol drops to obtain yellow solution in ice bath system；Stirred overnight at room temperature；After the product obtained rotation is evaporated solvent,
It is neutral with dilute hydrochloric acid, sodium bicarbonate, saturated nacl aqueous solution washing, then is dried overnight through anhydrous sodium sulfate；By concentrated solution mistake
Chromatographic column, obtains dark red oil；It is the RAFT agent containing terminal acetylene.
Preferably, the concentration of step (1) described sodium hydroxide solution 1 is 50%, sodium hydroxide solution 1 and tert-butyl mercaptan
Mole dosage ratio be 1: 1～1: 1.2, the time for adding of sodium hydroxide solution 1 controls 15～30min.
Preferably, the consumption of step (1) described distilled water 1 is to use 150ml distilled water according to every 1mol tert-butyl mercaptan
1；The consumption of described acetone is to use 50ml acetone according to every 1mol tert-butyl mercaptan；The consumption of described distilled water 2 is according to often
1mol tert-butyl mercaptan uses 150ml distilled water 2；The consumption of described distilled water 3 is to use according to every 1mol tert-butyl mercaptan
250ml distilled water 3.
Preferably, the concentration of step (1) described sodium hydroxide solution 2 is 50%, sodium hydroxide solution 2 and 2 bromopropionic acid
Mole dosage ratio is 1: 1～1: 1.2, and the time for adding of sodium hydroxide solution 2 controls 15～30min.
Preferably, the tert-butyl mercaptan described in step (1) is 1: 1～1: 1.2 with the mol ratio of Carbon bisulfide consumption；Described
Tert-butyl mercaptan is 1: 1～1: 1.1 with the mol ratio of 2 bromopropionic acid consumption；During described dropping 2 bromopropionic acid, system temperature is less than 20
℃；Time for adding is 15min～30min；Described dropping concentrated hydrochloric acid should make the pH value of system be 0～1.
Preferably, the RAFT agent containing terminal carboxyl group described in step (2) and 1-(3-dimethylamino-propyl)-3-second
Base carbodiimide hydrochloride (EDC HCl), the mole dosage ratio of DMAP (DMAP) be: 1 1.5 0.5～1 2
0.5。
Preferably, the RAFT agent containing terminal carboxyl group described in step (2) with the mole dosage ratio of propilolic alcohol is: 1
1.5～1 2.Preferably, the leacheate of the chromatographic column described in step (2) is petroleum ether and ethyl acetate, volume ratio be 60: 1～
30∶1。
The preparation process flow process of the above-mentioned RAFT agent containing terminal acetylene is as shown in Figure 1.
The above-mentioned RAFT agent containing terminal acetylene both can apply to RAFT polymerization, can be used to again and containing azido
The little molecule of group or polymer reaction, it is possible to achieve RAFT polymerization and the combination of click chemistry.
Compared with prior art, the present invention has the following advantages and beneficial effect: the one that the present invention designs contains Terminal Acetylenes
The RAFT agent of the structure of base: the S-tert-butyl group-S ,-isopropyl acid propine ester group trithiocarbonate, it is possible to well realize
The combination that click chemistry is polymerized with RAFT, thus block, graft polymers etc. are had the polymer of certain 26S Proteasome Structure and Function
Preparation provides the foundation.
Accompanying drawing explanation
Fig. 1 is the preparation process flow chart that the present invention contains the RAFT agent of terminal acetylene；
Fig. 2 is the product of step (1): the nuclear-magnetism figure of a kind of RAFT agent containing terminal carboxyl group；
Fig. 3 is the target product of the present invention: the nuclear-magnetism figure of a kind of RAFT agent containing terminal acetylene.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of preparation of the RAFT agent containing terminal carboxyl group:
(1) sodium hydroxide solution (4gNaOH, 0.1mol) that mass fraction is 50% is joined it is under stirring
Tert-butyl mercaptan (9.02g, 0.1mol) and distilled water (15ml) mixed solution in, be subsequently adding 5ml acetone, continue stirring
30min；Drip again in the system that Carbon bisulfide (8.37g, 0.11mol) cools down to ice bath and obtain orange solution；Continue to stir
Mix 30min, then drip 2 bromopropionic acid (15.30g, 0.10mol) in system, and maintain temperature below 20 DEG C, then drip
Mass fraction is the sodium hydroxide solution (4gNaOH, 0.1mol) of 50%, when system temperature is in room temperature, adds 15ml distillation
Water；Adding 25ml distilled water to system after stirring in water bath 24h under room temperature, holding system is under condition of ice bath, then drips 15ml
Concentrated hydrochloric acid solution, is acidity to system, and stirs holding system and maintain low temperature state；Dividing occur in yellow oil and aqueous solution
Layer, until grease becomes solid-state, after filtering, constantly rinses with cold distilled water, and room temperature in vacuo is dried.Product warp thick to yellow
Normal hexane is recrystallized to give glassy yellow acicular crystal, is the carboxylic RAFT agent of end.
A kind of preparation of the RAFT agent containing terminal acetylene:
(2) by RAFT agent (2.39g, 0.01mol) containing terminal carboxyl group obtained above, EDC HCl (2.88,
0.015mol), DMAP (0.61g, 0.005mol) three be stirred continuously in the dichloromethane of 100ml and blast argon 60min,
Propilolic alcohol (0.84g, 0.015mol) drips when system is in ice bath, and the yellow solution obtained at room temperature stirs
Mix 48h；Products therefrom, after hanging and boiling off solvent, is washed repeatedly with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated nacl aqueous solution
After washing as neutrality, then it is dried overnight through anhydrous magnesium sulfate；Concentrated solution is crossed chromatography silica gel post, and eluent is petroleum ether and acetic acid second
Ester, volume ratio is 60 1～30 1 changes, obtains dark red oil sterling.It is the RAFT chain containing terminal acetylene of the present invention
Transfer agent.
Use nuclear magnetic resonance analyser that the product of (1) Yu (2) is carried out respectively1H NMR (400M Hz, DMSO) analyzes, result
See accompanying drawing 2, Fig. 3.
Embodiment 2
A kind of preparation of the RAFT agent containing terminal carboxyl group:
(1) sodium hydroxide solution (4gNaOH, 0.1mol) that mass fraction is 50% is joined it is under stirring
Tert-butyl mercaptan (9.02g, 0.1mol) and distilled water (15ml) mixed solution in, add 5ml acetone, continue stirring
30min；The system that dropping Carbon bisulfide (9.14g, 0.12mol) cools down to ice bath obtains orange solution；Continue stirring
30min, then drip 2 bromopropionic acid (15.30g, 0.10mol) in system, and maintain temperature below 20 DEG C, then drip matter
Amount mark is the sodium hydroxide solution (4gNaOH, 0.1mol) of 50%, when system temperature is in room temperature, adds 15ml distillation
Water；Adding 25ml distilled water to system after stirring in water bath 24h under room temperature, holding system is under condition of ice bath, then drips 15ml
Concentrated hydrochloric acid solution, is acidity to system, and stirs holding system and maintain low temperature state；Dividing occur in yellow oil and aqueous solution
Layer, until grease becomes solid-state, after filtering, constantly rinses with cold distilled water, and room temperature in vacuo is dried.Product warp thick to yellow
Normal hexane is recrystallized to give glassy yellow acicular crystal, is the carboxylic RAFT agent of end.
A kind of preparation of the RAFT agent containing terminal acetylene:
(2) by RAFT agent (2.39g, 0.01mol) containing terminal carboxyl group obtained above, EDC HCl
(3.83g, 0.02mol), DMAP (0.61g, 0.005mol) three are stirred continuously in the dichloromethane of 100ml and blast argon
60min, propilolic alcohol (0.84g, 0.015mol) drips when system is in ice bath, and the yellow solution obtained is in room
48h is stirred under temperature；The product obtained until outstanding boil off solvent after, molten with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated sodium-chloride
After liquid cyclic washing is neutrality, then it is dried overnight through anhydrous magnesium sulfate；Concentrated solution is crossed chromatography silica gel post, and eluent is petroleum ether
With ethyl acetate, volume ratio is 60 1～30 1 changes, obtains dark red oil sterling.Be the present invention containing terminal acetylene
RAFT agent.
Use nuclear magnetic resonance analyser that the product of (1) Yu (2) is carried out respectively1H NMR (400M Hz, DMSO) analyzes, result
It is consistent with embodiment 1.
Embodiment 3
A kind of preparation of the RAFT agent containing terminal carboxyl group:
(1) sodium hydroxide solution (4gNaOH, 0.1mol) that mass fraction is 50% is joined it is under stirring
Tert-butyl mercaptan (9.02g, 0.1mol) and distilled water (15ml) mixed solution in, add 5ml acetone, continue stirring
30min；Drip again in the system that Carbon bisulfide (8.37g, 0.11mol) cools down to ice bath and obtain orange solution；Continue to stir
Mix 30min, then drip 2 bromopropionic acid (16.83g, 0.11mol) in system, and maintain temperature below 20 DEG C, then drip
Mass fraction is the sodium hydroxide solution (4gNaOH, 0.1mol) of 50%, when system temperature is in room temperature, adds 15ml distillation
Water；Adding 25ml distilled water to system after stirring in water bath 24h under room temperature, holding system is under condition of ice bath, then drips 15ml
Concentrated hydrochloric acid solution, is acidity to system, and stirs holding system and maintain low temperature state；Dividing occur in yellow oil and aqueous solution
Layer, until grease becomes solid-state, after filtering, constantly rinses with cold distilled water, and room temperature in vacuo is dried；Product warp thick to yellow
Normal hexane is recrystallized to give glassy yellow acicular crystal, is the carboxylic RAFT agent of end.
A kind of preparation of the RAFT agent containing terminal acetylene:
(2) by RAFT agent (2.39g, 0.01mol) containing terminal carboxyl group obtained above, EDC HCl (2.88,
0.015mol), DMAP (0.61g, 0.005mol) three be stirred continuously in the dichloromethane of 100ml and blast argon 60min,
Propilolic alcohol (1.12g, 0.02mol) drips when system is in ice bath, and the yellow solution obtained at room temperature stirs
Mix 48h；The product obtained is after hanging and boiling off solvent, with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated nacl aqueous solution repeatedly
After washing is for neutrality, then it is dried overnight through anhydrous magnesium sulfate；Concentrated solution is crossed chromatography silica gel post, and eluent is petroleum ether and acetic acid
Ethyl ester, volume ratio is 60 1～30 1 changes, obtains dark red oil sterling, is the RAFT containing terminal acetylene of the present invention
Chain-transferring agent.
Use nuclear magnetic resonance analyser that the product of (1) Yu (2) is carried out respectively1H NMR (400M Hz, DMSO) analyzes, result
It is consistent with embodiment 1.
Embodiment 4
A kind of preparation of the RAFT agent containing terminal carboxyl group:
(1) sodium hydroxide solution (4gNaOH, 0.1mol) that mass fraction is 50% is joined it is under stirring
Tert-butyl mercaptan (9.02g, 0.1mol) and distilled water (15ml) mixed solution in, add 5ml acetone, continue stirring
30min；Drip again in the system that Carbon bisulfide (9.14g, 0.12mol) cools down to ice bath and obtain orange solution；Continue to stir
Mix 30min, then drip 2 bromopropionic acid (16.83g, 0.11mol) in system, and maintain temperature below 20 DEG C, then drip
Mass fraction is the sodium hydroxide solution (4gNaOH, 0.1mol) of 50%, when system temperature is in room temperature, adds 15ml distillation
Water；Adding 25ml distilled water to system after stirring in water bath 24h under room temperature, holding system is under condition of ice bath, then drips 15ml
Concentrated hydrochloric acid solution, is acidity to system, and stirs holding system and maintain low temperature state；Dividing occur in yellow oil and aqueous solution
Layer, until grease becomes solid-state, after filtering, constantly rinses with cold distilled water, and room temperature in vacuo is dried；Product warp thick to yellow
Normal hexane is recrystallized to give glassy yellow acicular crystal, is the carboxylic RAFT agent of end.
A kind of preparation of the RAFT agent containing terminal acetylene:
(2) by RAFT agent (2.39g, 0.01mol) containing terminal carboxyl group obtained above, EDC HCl (3.83,
0.02mol), DMAP (0.61g, 0.005mol) three be stirred continuously in the dichloromethane of 100ml and blast argon 60min,
Propilolic alcohol (1.12g, 0.02mol) drips when system is in ice bath, and the yellow solution obtained at room temperature stirs
Mix 48h；The product obtained is after hanging and boiling off solvent, with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated nacl aqueous solution repeatedly
After washing is for neutrality, then it is dried overnight through anhydrous magnesium sulfate；Concentrated solution is crossed chromatography silica gel post, and eluent is petroleum ether and acetic acid
Ethyl ester, volume ratio is 60 1～30 1 changes, obtains dark red oil sterling, is the RAFT containing terminal acetylene of the present invention
Chain-transferring agent.
Use nuclear magnetic resonance analyser that the product of (1) Yu (2) is carried out respectively1H NMR (400M Hz, DMSO) analyzes, result
It is consistent with embodiment 1.
Embodiment 5
A kind of preparation of the RAFT agent containing terminal carboxyl group:
(1) sodium hydroxide solution (8gNaOH, 0.22mol) that mass fraction is 50% is joined it is under stirring
Tert-butyl mercaptan (18.04g, 0.2mol) and distilled water (30ml) mixed solution in, add 10ml acetone, continue stirring
30min；Drip again in the system that Carbon bisulfide (18.27g, 0.12mol) cools down to ice bath and obtain orange solution；Continue to stir
Mix 30min, then drip 2 bromopropionic acid (33.66g, 0.11mol) in system, and maintain temperature below 20 DEG C, then drip
Mass fraction is the sodium hydroxide solution (8.8gNaOH, 0.22mol) of 50%, when system temperature is in room temperature, adds 30ml
Distilled water；Adding 25ml distilled water to system after stirring in water bath 24h under room temperature, holding system is under condition of ice bath, then drips
30ml concentrated hydrochloric acid solution, is acidity to system, and stirs holding system and maintain low temperature state；Yellow oil goes out with aqueous solution
Now layering is until grease becomes solid-state, after filtering, constantly rinses with cold distilled water, and room temperature in vacuo is dried；Product thick to yellow
Product are recrystallized to give glassy yellow acicular crystal through normal hexane, are the carboxylic RAFT agent of end.
A kind of preparation of the RAFT agent containing terminal acetylene:
(2) by RAFT agent (11.92g, 0.05mol) containing terminal carboxyl group obtained above, EDC HCl
(19.17,0.1mol), DMAP (3.05g, 0.025mol) three are stirred continuously in the dichloromethane of 100ml and blast argon
60min, propilolic alcohol (4.20g, 0.075mol) drips when system is in ice bath, and the yellow solution obtained is in room
48h is stirred under temperature；The product obtained until outstanding boil off solvent after, molten with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated sodium-chloride
After liquid cyclic washing is neutrality, then it is dried overnight through anhydrous magnesium sulfate；Concentrated solution is crossed chromatography silica gel post, and eluent is petroleum ether
With ethyl acetate, volume ratio be 60 1～30 1 change, obtain dark red oil sterling, be the present invention containing terminal acetylene
RAFT agent.
Use nuclear magnetic resonance analyser that the product of (1) Yu (2) is carried out respectively1H NMR (400M Hz, DMSO) analyzes, result
It is consistent with embodiment 1.
Embodiment 6
A kind of preparation of the RAFT agent containing terminal carboxyl group:
(1) sodium hydroxide solution (16gNaOH, 0.4mol) that mass fraction is 50% is joined it is under stirring
Tert-butyl mercaptan (36.07g, 0.4mol) and distilled water (60ml) mixed solution in, add 20ml acetone, continue stirring
30min；Drip again in the system that Carbon bisulfide (18.27g, 0.12mol) cools down to ice bath and obtain orange solution；Continue to stir
Mix 30min, then drip 2 bromopropionic acid (33.66g, 0.11mol) in system, and maintain temperature below 20 DEG C, then drip
Mass fraction is sodium hydroxide solution (8gNaOH, the 12gH of 50%2O), when system temperature is in room temperature, add 30ml distillation
Water；Adding 25ml distilled water to system after stirring in water bath 24h under room temperature, holding system is under condition of ice bath, then drips 30ml
Concentrated hydrochloric acid solution, is acidity to system, and stirs holding system and maintain low temperature state；Dividing occur in yellow oil and aqueous solution
Layer, until grease becomes solid-state, after filtering, constantly rinses with cold distilled water, and room temperature in vacuo is dried；Product warp thick to yellow
Normal hexane is recrystallized to give glassy yellow acicular crystal, is the carboxylic RAFT agent of end.
A kind of preparation of the RAFT agent containing terminal acetylene:
(2) by RAFT agent (11.92g, 0.05mol) containing terminal carboxyl group obtained above, EDC HCl
(19.17,0.1mol), DMAP (3.05g, 0.025mol) three are stirred continuously in the dichloromethane of 100ml and blast argon
60min, propilolic alcohol (5.61g, 0.1mol) drips when system is in ice bath, and the yellow solution obtained is in room temperature
Lower stirring 48h；The product obtained is after hanging and boiling off solvent, with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated nacl aqueous solution
After cyclic washing is neutrality, then it is dried overnight through anhydrous magnesium sulfate；Concentrated solution is crossed chromatography silica gel post, eluent be petroleum ether with
Ethyl acetate, volume ratio is 60 1～30 1 changes, obtain dark red oil sterling, be the present invention containing terminal acetylene
RAFT agent.
Use nuclear magnetic resonance analyser that the product of (1) Yu (2) is carried out respectively1H NMR (400M Hz, DMSO) analyzes, result
It is consistent with embodiment 1.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the RAFT agent containing terminal acetylene, it is characterised in that: this RAFT agent has and is shown below
Structure:
The preparation method of a kind of RAFT agent containing terminal acetylene the most according to claim 1, it is characterised in that bag
Include following steps: (1), with tert-butyl mercaptan as initiation material, generates mercaptides under the effect of alkali, then with Carbon bisulfide effect,
Generate trithiocarbonate；Gained trithiocarbonate reacts with 2 bromopropionic acid under the catalytic action of alkali, after acidifying
To the RAFT agent containing end carboxyl；(2) by the RAFT agent containing end carboxyl of (1) gained through normal hexane recrystallization
After, under the effect of 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride and DMAP and propilolic alcohol
Esterification generates a kind of trithiocarbonate containing end alkynyl radical, by crude product by experimental techniques such as extraction, column chromatographies, finally gives
RAFT agent containing terminal acetylene.
The preparation method of a kind of RAFT agent containing terminal acetylene the most according to claim 1, it is characterised in that tool
Body comprises the steps:
(1) sodium hydroxide solution 1 is dropped in the mixed solution of tert-butyl mercaptan and the distilled water 1 being under stirring,
Generate mercaptides；Then drip acetone, obtain colourless transparent solution, then drip in the system that Carbon bisulfide cools down to ice bath
Obtain orange solution；After stirring, then dripping 2 bromopropionic acid in system, then dropping sodium hydroxide solution 2, treats temperature stabilization,
Add distilled water 2 to be diluted；After reaction overnight is stirred at room temperature；In system, add distilled water 3 dilute, drip dense under condition of ice bath
Hydrochloric acid makes system be acidity and stir, and yellow oil occurs, continues stirring until grease becomes solid-state；After sucking filtration, use cold steaming
Distilled water is constantly rinsed, and dried and recrystallization must contain the RAFT agent of terminal carboxyl group；
(2) by the RAFT agent containing terminal carboxyl group of step (1) gained and 1-(3-dimethylamino-propyl)-3-ethyl carbon two
Inferior amine salt hydrochlorate dissolves with DMAP dichloromethane, is stirred continuously and blasts argon, and propilolic alcohol drops to ice bath
System obtains yellow solution；Stirred overnight at room temperature；After the product obtained rotation is evaporated solvent, with dilute hydrochloric acid, sodium bicarbonate, satisfy
It is neutrality with sodium chloride solution washing, then is dried overnight through anhydrous sodium sulfate；Concentrated solution is crossed chromatographic column, obtains dark red oil
Thing；It is the RAFT agent containing terminal acetylene.
The preparation method of a kind of RAFT agent containing terminal acetylene the most according to claim 3, it is characterised in that: step
Suddenly the concentration of (1) described sodium hydroxide solution 1 is mass fraction 50%, sodium hydroxide solution 1 and tert-butyl mercaptan mole with
Amount ratio is 1: 1～1: 1.2, and the time for adding of sodium hydroxide solution 1 controls 15～30min；Described sodium hydroxide solution 2 dense
Degree is mass fraction 50%, and sodium hydroxide solution 2 and the mole dosage ratio of 2 bromopropionic acid are 1: 1～1: 1.2, sodium hydroxide solution
The time for adding of 2 controls 15～30min.
The preparation method of a kind of RAFT agent containing terminal acetylene the most according to claim 3, it is characterised in that: step
Suddenly the consumption of (1) described distilled water 1 is to use 150ml distilled water 1 according to every 1mol tert-butyl mercaptan；The consumption of described acetone is
50ml acetone is used according to every 1mol tert-butyl mercaptan；The consumption of described distilled water 2 is to use according to every 1mol tert-butyl mercaptan
150ml distilled water 2；The consumption of described distilled water 3 is to use 250ml distilled water 3 according to every 1mol tert-butyl mercaptan.
The preparation method of a kind of RAFT agent containing terminal acetylene the most according to claim 3, it is characterised in that: step
Suddenly the tert-butyl mercaptan described in (1) is 1: 1～1: 1.2 with the mol ratio of Carbon bisulfide consumption；Described tert-butyl mercaptan and 2-bromine
The mol ratio of propanoic acid consumption is 1: 1～1: 1.1；During described dropping 2 bromopropionic acid, system temperature is less than 20 DEG C；Time for adding is
15min～30min；Described dropping concentrated hydrochloric acid should make the pH value of system be 0～1.
The preparation method of a kind of RAFT agent containing terminal acetylene the most according to claim 3, it is characterised in that: step
Suddenly the RAFT agent containing terminal carboxyl group described in (2), 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride
The mole dosage ratio of (EDC HCl), DMAP (DMAP) is: 1 1.5 0.5 1.0～1 2 0.5.
The preparation method of a kind of RAFT agent containing terminal acetylene the most according to claim 3, it is characterised in that: step
Suddenly the RAFT agent containing terminal carboxyl group described in (2) with the mole dosage ratio of propilolic alcohol is: 1 1.5～1 2.
The preparation method of a kind of RAFT agent containing terminal acetylene the most according to claim 3, it is characterised in that: step
Suddenly the leacheate of the chromatographic column described in (2) is petroleum ether and ethyl acetate, and volume ratio is 60: 1～30: 1.
A kind of RAFT agent containing terminal acetylene the most according to claim 1 realizes RAFT polymerization and point at the same time
Hit the application in reaction.
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