CN103304798A - ATRP (Atom Transfer Radical Polymerization) reagent based on low molecular weight carbon dioxide copolymer and preparation method of ATRP reagent - Google Patents
ATRP (Atom Transfer Radical Polymerization) reagent based on low molecular weight carbon dioxide copolymer and preparation method of ATRP reagent Download PDFInfo
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Abstract
The invention provides an ATRP (Atom Transfer Radical Polymerization) reagent based on a low molecular weight carbon dioxide copolymer and a preparation method of the ATRP reagent. The ATRP reagent is obtained through reaction between a low molecular weight carbon dioxide and epoxy compound copolymer with terminal alcohol hydroxide and halogen acyl halide. The preparation method comprises the following steps of: dissolving the low molecular weight carbon dioxide copolymer into an aromatic hydrocarbon solvent, introducing nitrogen, bubbling and enabling a proper amount of solvent to be evaporated; cooling to 0 DEG C and adding an organic amino or pyridine compound as an acid-binding agent; adding the halogen acyl halide, after the reaction is thorough, standing for filtering out undissolved solid substances, and distilling and recovering aromatic hydrocarbon in filtrate to obtain a crude product of the RTRP reagent; dissolving the crude product into a dichloromethane solvent, then washing, and collecting an organic layer; and dehydrating and drying the organic layer, and distilling and removing dichloromethane to obtain the ATRP reagent. The ATRP reagent can be used for reducing the emission of carbon dioxide as greenhouse gas and maintaining the balance of carbon circulation in the ecological environment and the sustainable development; and the preparation method and process are simple and easy to control.
Description
[technical field]
The present invention relates to a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer and preparation method thereof.
[background technology]
Be that the carbon dioxide copolymer of representative is a kind of biodegradable material of synthetic of cheapness with carbonic acid gas and epoxy compounds copolymerization, have the value of large-scale production and be expected to and obtain to use at aspects such as bio-medical and food product pack.Wherein, the application of lower molecular weight carbon dioxide copolymer resin causes people's attention in recent years: application number is 201010224108.0 Chinese patent, discloses a kind of poly carboxylic acid series water reducer and synthetic method thereof that contains the lower molecular weight carbon dioxide copolymer; Application number is 200710055211.5 Chinese patent, discloses a kind of method of using lower molecular weight carbonic acid gas-epoxy compounds copolymer full-biological degradation nonwoven cloth.
On the other hand, atom transition free radical polymerization reaction is widely used in molecular designing and controlled the constructing of polycomponent block polymer, the atom transition free radical polymerization reaction reagent that is applicable to different initiator systems, different polymerization reaction monomers is by deep research and reach its maturity, but does not appear in the newspapers as yet based on exploitation of the atom transition free radical polymerization reaction reagent of lower molecular weight carbon dioxide copolymer and preparation method thereof.Carry out the synthetic and polyreaction research of atom transition free radical polymerization reaction reagent based on the lower molecular weight carbon dioxide copolymer ATRP reagent of lower molecular weight carbon dioxide copolymer (namely based on), have very large meaning.
[summary of the invention]
One of the technical problem to be solved in the present invention, be to provide a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer, this ATRP reagent is a kind of means of effectively utilizing the lower molecular weight carbon dioxide copolymer, the greenhouse gases emission of carbon-dioxide be can reduce, carbon cycle balance and sustainable development in the ecotope safeguarded.
The present invention realizes one of above-mentioned technical problem like this:
A kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer, the structural formula of the molecule of described ATRP reagent are at least a in the following molecular structural formula:
Wherein: x
1, x
2〉=1 positive integer;
0≥k≥4，0≥s≥4；
Has a non-vanishing positive integer among m and the n at least;
m
1And n
1In have at least one to be non-vanishing positive integer;
y
1, y
2, p, p
1, q, q
1Be 0 or positive integer;
R=H, CH
3Or phenyl;
R
1, R
2=H or CH
3
X=Cl, or Br, or CH
2Cl, or CH
2Br.
Further, described ATRP reagent is to be obtained by the lower molecular weight carbonic acid gas-epoxy compound composition copolymer with terminal alcohol hydroxyl and halogen acyl halide reaction; The number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～30000.
Further, the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～18000.
Two of the technical problem to be solved in the present invention is to provide a kind of preparation method of the ATRP reagent based on the lower molecular weight carbon dioxide copolymer, and this preparation method's flow process is simple, easy to control.
The present invention realizes two of above-mentioned technical problem like this:
A kind of preparation method of the ATRP reagent based on the lower molecular weight carbon dioxide copolymer comprises the steps:
The lower molecular weight carbon dioxide copolymer under agitation is dissolved in the anhydrous aromatic hydrocarbon solvent, is made into 3～50w
tThe solution of %, logical nitrogen bubble is after 10～60 minutes, heat temperature raising to 90～210 ℃, and steam total solvent amount 10～40w
tThe aromatic hydrocarbon of %;
Continuation under logical condition of nitrogen gas, be cooled to 0 ℃ and add organic amine or pyridine compounds and their as acid binding agent, perhaps will react the acid tail gas of the hydrogen halide that generates and import the alkali lye absorption;
Then, in above-mentioned solution, add halogen acyl halide, treat that halogen acyl halide dropwises the back and keep to stir and to make it to react completely, leave standstill, the solids removed by filtration insolubles, and with the distillation of the anhydrous aromatic hydrocarbon in filtrate recovery, obtain the ATRP reagent crude product based on the lower molecular weight carbon dioxide copolymer;
To be dissolved in dichloromethane solvent based on the ATRP reagent crude product of lower molecular weight carbon dioxide copolymer, be made into 3～60w
tThe solution of % respectively washs 2～3 times collected organic layer then successively with saturated ammonium chloride solution, saturated sodium bicarbonate solution and water;
Dewater organic layer dry and after distillation removed methylene dichloride, products therefrom namely was based on the ATRP reagent of lower molecular weight carbon dioxide copolymer.
Further, described lower molecular weight carbon dioxide copolymer has the terminal alcohol hydroxyl, and its molecular structural formula is at least a kind of in the following molecular structural formula:
Wherein: x, the integer of x1 〉=1;
M and n can not be 0 integer simultaneously; M1 and n1 can not be 0 integer simultaneously;
y
1, y
2, p, p1, q, the integer of q1 〉=0; R=H, CH
3, or phenyl.
Further, the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～30000.
Further, the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～18000.
Further, described aromatic hydrocarbon is at least a in dimethylbenzene, o-Xylol, p-Xylol, m-xylene, toluene, the benzene.
Further, described organic amine is at least a in triethylamine, three n-propyl amine, tri-n-butyl amine, the three positive decyl amine.
Further, described pyridine compounds and their be 2-methoxypyridine, 2-methylamino pyridine, 3-picoline, 3-amido pyridine, 3-pyridone, 3-phenylpyridine, pyridine, at least a in Dimethylamino pyridine, 4-picoline, the 4-tert .-butylpyridine.
Further, described halogen acyl halide is 2-bromo-2-methyl-prop acyl chlorides, 2-bromo-2-methyl-prop acylbromide, 2-chloro-2-methyl-prop acylbromide, 2-chloro-2-methyl-prop acyl chlorides, chloro-acetyl chloride, the chloro acetyl bromide, bromo acetyl bromide, the bromo Acetyl Chloride 98Min., 2 bromo propionyl bromide, the 2-bromo propionyl chloro, 2-chlorine propionyl bromide, the 2-chlorpromazine chloride, the 3-bromopropionyl bromide, the 3-bromo propionyl chloro, the 3-chlorpromazine chloride, 3-chlorine propionyl bromide, 4-bromine butyryl bromide, the 4-bromobutanoylchloride, 4-neoprene acylbromide, the 4-chlorobutanoylchloride, 5-bromine bromine pivaloyl, 5-chlorine valeryl chloride, 5-bromine valeryl chloride, 5-chlorine bromine pivaloyl, Chloropivaloyl chloride, chloro pivaloyl bromine, the bromo pivaloyl chloride, the bromo pivaloyl chloride, 6-bromine hexanoyl bromide, 6-bromine caproyl chloride, 6-chlorine hexanoyl bromide, at least a in the 6-chlorine caproyl chloride.
Further, described halogen acyl halide is at least a in 2-bromo-2-methyl-prop acylbromide, 2-bromo-2-methyl-prop acyl chlorides, 2-chloro-2-methyl-prop acyl chlorides, 2-chloro-2-methyl-prop acylbromide, 2 bromo propionyl bromide, 2-bromo propionyl chloro, 2-chlorpromazine chloride, 2-chlorine propionyl bromide, chloro-acetyl chloride, chloro acetyl bromide, bromo acetyl bromide, the bromo Acetyl Chloride 98Min..
Further, the amount of substance of described lower molecular weight carbon dioxide copolymer and halogen acyl halide and organic amine or pyridine compounds and their is such as following:
Lower molecular weight carbon dioxide copolymer: halogen acyl halide: organic amine or pyridine compounds and their=1: 1～3: 0～3.2.
The present invention has following advantage:
The present invention is a kind of means of effectively utilizing the lower molecular weight carbon dioxide copolymer, thereby reduces the greenhouse gases emission of carbon-dioxide, safeguards balance and the sustainable development of carbon cycle in the ecotope; And preparation flow of the present invention is simple, easy to control.
Application based on the atom transition free radical polymerization reaction reagent (ATRP reagent) of lower molecular weight carbon dioxide copolymer, be the effective means of constructing the segmented copolymer that contains the carbon dioxide copolymer segment, this based block copolymer is expected to widely use in new bio medical material, novel degraded type material field.
[description of drawings]
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is embodiments of the invention 3
1H NMR spectrogram synoptic diagram.
[embodiment]
See also shown in Figure 1ly, embodiments of the invention are described in detail.
The present invention relates to a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer (being atom transition free radical polymerization reaction reagent), the structural formula of described ATRP reagent is at least a in the following molecular structural formula:
Wherein: x
1, x
2〉=1 positive integer;
0≥k≥4，0≥s≥4；
Has a non-vanishing positive integer among m and the n at least;
m
1And n
1In have at least one to be non-vanishing positive integer;
y
1, y
2, p, p
1, q, q
1Be 0 or positive integer;
R=H, CH
3, or phenyl; R
1, R
2=H or CH
3
X=Cl, or Br, or CH
2Cl, or CH
2Br.
The invention still further relates to the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer (being atom transition free radical polymerization reaction reagent), comprise the steps:
The lower molecular weight carbon dioxide copolymer under agitation is dissolved in the anhydrous aromatic hydrocarbon solvent, is made into 3～50w
tThe solution of %, logical nitrogen bubble is after 10～60 minutes, heat temperature raising to 90～210 ℃, and steam total solvent amount 10～40w
tThe aromatic hydrocarbon of %;
Continuation under logical condition of nitrogen gas, be cooled to 0 ℃ and add organic amine or pyridine compounds and their as acid binding agent, perhaps will react the acid tail gas of the hydrogen halide that generates and import the alkali lye absorption;
Then, in above-mentioned solution, add halogen acyl halide, treat that halogen acyl halide dropwises the back and keep to stir and to make it to react completely, leave standstill, the solids removed by filtration insolubles, and with the distillation of the anhydrous aromatic hydrocarbon in filtrate recovery, obtain the ATRP reagent crude product based on the lower molecular weight carbon dioxide copolymer;
ATRP reagent crude product is dissolved in dichloromethane solvent, is made into 3～60w
tThe solution of % respectively washs 2～3 times collected organic layer then successively with saturated ammonium chloride solution, saturated sodium bicarbonate solution and water;
Dewater organic layer dry and after distillation removed methylene dichloride, products therefrom namely was based on the ATRP reagent of lower molecular weight carbon dioxide copolymer.
Described described ATRP reagent based on the lower molecular weight carbon dioxide copolymer is to be obtained by the lower molecular weight carbonic acid gas-epoxy compound composition copolymer with terminal alcohol hydroxyl and halogen acyl halide reaction; The number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～30000.
Described lower molecular weight carbon dioxide copolymer has the terminal alcohol hydroxyl, and its molecular structural formula is at least a kind of in the following molecular structural formula:
Wherein: x, the integer of x1 〉=1; M and n can not be 0 integer simultaneously; M1 and n1 can not be 0 integer simultaneously; y
1, y
2, p, p1, q, the integer of q1 〉=0; R=H, CH
3, or phenyl.
More excellent, the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300-18000.
Described anhydrous aromatic hydrocarbon is at least a in dimethylbenzene, o-Xylol, p-Xylol, m-xylene, toluene, the benzene.
Described organic amine is at least a in triethylamine, three n-propyl amine, tri-n-butyl amine, the three positive decyl amine.
Described pyridine compounds and their is 2-methoxypyridine, 2-methylamino pyridine, 3-picoline, 3-amido pyridine, 3-pyridone, 3-phenylpyridine, pyridine, at least a in Dimethylamino pyridine, 4-picoline, the 4-tert .-butylpyridine.
Described halogen acyl halide is 2-bromo-2-methyl-prop acyl chlorides, 2-bromo-2-methyl-prop acylbromide, 2-chloro-2-methyl-prop acylbromide, 2-chloro-2-methyl-prop acyl chlorides, chloro-acetyl chloride, the chloro acetyl bromide, bromo acetyl bromide, the bromo Acetyl Chloride 98Min., 2 bromo propionyl bromide, the 2-bromo propionyl chloro, 2-chlorine propionyl bromide, the 2-chlorpromazine chloride, the 3-bromopropionyl bromide, the 3-bromo propionyl chloro, the 3-chlorpromazine chloride, 3-chlorine propionyl bromide, 4-bromine butyryl bromide, the 4-bromobutanoylchloride, 4-neoprene acylbromide, the 4-chlorobutanoylchloride, 5-bromine bromine pivaloyl, 5-chlorine valeryl chloride, 5-bromine valeryl chloride, 5-chlorine bromine pivaloyl, Chloropivaloyl chloride, chloro pivaloyl bromine, the bromo pivaloyl chloride, the bromo pivaloyl chloride, 6-bromine hexanoyl bromide, 6-bromine caproyl chloride, 6-chlorine hexanoyl bromide, at least a in the 6-chlorine caproyl chloride;
More excellent, described halogen acyl halide is at least a in 2-bromo-2-methyl-prop acylbromide, 2-bromo-2-methyl-prop acyl chlorides, 2-chloro-2-methyl-prop acyl chlorides, 2-chloro-2-methyl-prop acylbromide, 2 bromo propionyl bromide, 2-bromo propionyl chloro, 2-chlorpromazine chloride, 2-chlorine propionyl bromide, chloro-acetyl chloride, chloro acetyl bromide, bromo acetyl bromide, the bromo Acetyl Chloride 98Min..
The amount of substance of described lower molecular weight carbon dioxide copolymer and halogen acyl halide and organic amine or pyridine compounds and their is such as following:
Lower molecular weight carbon dioxide copolymer: halogen acyl halide: organic amine or pyridine compounds and their=1: 1～3: 0～3.2.
The preparation feedback equation of described ATRP reagent based on the lower molecular weight carbon dioxide copolymer is as follows:
Wherein: 0 〉=k 〉=4; R
1, R
2=H or CH
3X '=Cl, or Br;
X=Cl, or Br, or CH
2Cl, or CH
2Br.
Be described further below in conjunction with the present invention of embodiment.
Embodiment 1: 10mmol lower molecular weight carbon dioxide copolymer (Mn=2500) under agitation is dissolved in the 300ml dry toluene solvent, and logical nitrogen bubble is after 20 minutes, and the rising temperature is to 130-180 ℃, and steams 50ml toluene; Under the logical condition of nitrogen gas of maintenance, be cooled to 0 ℃ and the pyridine that adds 26mmol as acid binding agent; The 2-chloro-2-methyl-prop acylbromide that adds 26mmol in the above-mentioned solution, treat that 2-chloro-2-methyl-prop acylbromide dropwises the back and keeps stirring to make it to react completely, leave standstill then, the solids removed by filtration insolubles, and with solvent distillation recovery, obtain the ATRP reagent crude product based on the lower molecular weight carbon dioxide copolymer.This crude product is dissolved in the dichloromethane solvent of 200ml, respectively washs collected organic layer 3 times with the saturated ammonium chloride solution of 60ml, the saturated sodium bicarbonate solution of 60ml and the water of 60ml successively then; With organic layer dewater drying and distill desolventizing after, products therefrom namely is based on the atom transition free radical polymerization reaction reagent of lower molecular weight carbon dioxide copolymer.
Embodiment 2: 10mmol lower molecular weight carbon dioxide copolymer (Mn=3000) under agitation is dissolved in (V in 350ml dry toluene/dimethylbenzene mixed solvent
Toluene/ V
Dimethylbenzene=50/50) logical nitrogen bubble was warming up to 130-210 ℃ after 30 minutes, steamed the solvent of 60ml, was keeping being cooled to 0 ℃ under the logical condition of nitrogen gas; Then, the 2-bromo-2-methyl-prop acylbromide that adds 26mmol, and will react the absorption of the acid tail gas importing of the hydrogen halide that generates alkali lye, after treating that 2-bromo-2-methyl-prop acylbromide dropwises, keep stirring and make it to react completely, leave standstill then, the solids removed by filtration insolubles, and solvent distillation reclaimed, obtain the ATRP reagent crude product based on the lower molecular weight carbon dioxide copolymer; This crude product is dissolved in the dichloromethane solvent of 270ml, respectively washs collected organic layer 3 times with the saturated ammonium chloride solution of 20ml, the saturated sodium hydrogen carbonate solution of 20ml and the water of 20ml successively then; With organic layer dewater drying and distill desolventizing after, products therefrom namely is based on the atom transition free radical polymerization reaction reagent of lower molecular weight carbon dioxide copolymer.
Embodiment 3: be dissolved in the 250ml dry toluene solvent under 9.6mmol carbon dioxide-epoxy propane copolymer (Mn=2500) is stirred, logical nitrogen bubble was warming up to 130-180 ℃ after 30 minutes, steamed 50ml toluene; Under the logical condition of nitrogen gas of maintenance, be cooled to 0 ℃ and the triethylamine that adds 30mmol as acid binding agent; Drip the 2 bromo propionyl bromide of 30mmol again in the solution that adds acid binding agent, treat that 2 bromo propionyl bromide dropwises the back and keeps stirring to make it to react completely, leave standstill then, the solids removed by filtration insolubles, and with solvent distillation recovery, obtain the ATRP reagent crude product based on the lower molecular weight carbon dioxide copolymer.This crude product is dissolved in the dichloromethane solvent of 150ml, respectively washs collected organic layer 2 times with saturated ammonium chloride solution, the 40ml of 40ml saturated sodium hydrogen carbonate solution and 40ml water successively then; With organic layer dewater drying and distill desolventizing after, products therefrom namely is based on the atom transition free radical polymerization reaction reagent of lower molecular weight carbon dioxide copolymer.
Embodiment 4: 10mmol lower molecular weight carbon dioxide copolymer (Mn=8000) under agitation is dissolved in the 460ml dry toluene solvent, logical nitrogen bubble is after 30 minutes, be warming up to 130-180 ℃, after steaming 60ml toluene, continuing to be cooled under the logical condition of nitrogen gas 0 ℃ and the triethylamine that adds 25mmol as acid binding agent; Drip the 2-chlorpromazine chloride of 25mmol in the solution that adds acid binding agent, treat that the 2-chlorpromazine chloride dropwises the back and keeps stirring to make it to react completely, leave standstill then, the solids removed by filtration insolubles, and with solvent distillation recovery, obtain the ATRP reagent crude product based on the lower molecular weight carbon dioxide copolymer.This crude product is dissolved in the dichloromethane solvent of 300ml, respectively washs collected organic layer 3 times with saturated ammonium chloride solution, the 50ml of 50ml saturated sodium hydrogen carbonate solution and 50ml water successively then; Dewater organic layer dry and after distillation removed methylene dichloride, products therefrom namely was based on the atom transition free radical polymerization reaction reagent of lower molecular weight carbon dioxide copolymer.
Embodiment 5: 15mmol lower molecular weight carbon dioxide copolymer (Mn=3000) under agitation is dissolved in (V in 350ml dry toluene/dimethylbenzene mixed solvent
Toluene/ V
Dimethylbenzene=30/70) logical nitrogen bubble was warming up to 130-180 ℃ after 30 minutes, steam 70ml toluene after, under logical condition of nitrogen gas, be cooled to 0 ℃ and add the pyridine of 33mmol; Drip the 2-bromo-2-methyl-prop acyl chlorides of 33mmol again, after treating that 2-bromo-2-methyl-prop acyl chlorides dropwises, keep to stir and to make it to react completely, leave standstill then, the solids removed by filtration insolubles, and with solvent distillation recovery, obtain the ATRP reagent crude product based on the lower molecular weight carbon dioxide copolymer.This crude product is dissolved in the dichloromethane solvent of 350ml, respectively washs collected organic layer 3 times with the saturated ammonium chloride solution of 40ml, saturated sodium hydrogen carbonate solution and water successively then; With organic layer dewater drying and distill desolventizing after, product namely is based on the ATRP reagent of lower molecular weight carbon dioxide copolymer.
Fig. 1 is the embodiment of the invention 3
1H NMR spectrogram synoptic diagram, wherein spectral line (1) is the lower molecular weight carbon dioxide-epoxy propane copolymer; Spectral line (2) is the ATRP reagent based on the lower molecular weight carbon dioxide-epoxy propane copolymer.
Among Fig. 1, be positioned at the signal peak of 4.2ppm and 4.8-5.0ppm, they are respectively CH in the carbon dioxide-epoxy propane copolymer molecular chain ester units structure
2(b) and the characteristic absorbance of CH (a); Being positioned at the signal peak at 3.4-3.8ppm place, is CH in the propylene oxide homopolymerization product ether segment structure
2The characteristic peak of (b ') and CH (a '); The signal peak that is positioned at the 1.75ppm place in the spectral line 2 is CH
3(c) characteristic peak shows that the last material that generates of this reaction is based on the ATRP reagent of lower molecular weight carbon dioxide-epoxy propane copolymer.
The present invention is a kind of means of effectively utilizing the lower molecular weight carbon dioxide copolymer, thereby reduces the greenhouse gases emission of carbon-dioxide, safeguards balance and the sustainable development of carbon cycle in the ecotope; And preparation flow of the present invention is simple, easy to control.
Application based on the atom transition free radical polymerization reaction reagent (ATRP reagent) of lower molecular weight carbon dioxide copolymer, be the effective means of constructing the segmented copolymer that contains the carbon dioxide copolymer segment, this based block copolymer is expected to widely use in new bio medical material, novel degraded type material field.
Though more than described the specific embodiment of the present invention; but being familiar with those skilled in the art is to be understood that; our described specific embodiment is illustrative; rather than for the restriction to scope of the present invention; those of ordinary skill in the art are in modification and the variation of the equivalence of doing according to spirit of the present invention, all should be encompassed in the scope that claim of the present invention protects.
Claims (13)
1. ATRP reagent based on the lower molecular weight carbon dioxide copolymer is characterized in that: the molecular structural formula of described ATRP reagent is at least a kind of in the following molecular structural formula:
Wherein: x
1, x
2〉=1 positive integer;
0≥k≥4，0≥s≥4；
Has a non-vanishing positive integer among m and the n at least;
m
1And n
1In have at least one to be non-vanishing positive integer;
y
1, y
2, p, p
1, q, q
1Be 0 or positive integer;
R=H, CH
3Or phenyl; R
1, R
2=H or CH
3
X=Cl, or Br, or CH
2Cl, or CH
2Br.
2. a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer as claimed in claim 1 is characterized in that: described ATRP reagent is to be obtained by the lower molecular weight carbonic acid gas-epoxy compound composition copolymer with terminal alcohol hydroxyl and halogen acyl halide reaction; The number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～30000.
3. a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer as claimed in claim 2, it is characterized in that: the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～18000.
4. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer as claimed in claim 1 is characterized in that: comprise the steps:
The lower molecular weight carbon dioxide copolymer under agitation is dissolved in the anhydrous aromatic hydrocarbon solvent, is made into 3～50w
tThe solution of %, logical nitrogen bubble is after 10～60 minutes, heat temperature raising to 90～210 ℃, and steam total solvent amount 10～40w
tThe aromatic hydrocarbon of %;
Continuation under logical condition of nitrogen gas, be cooled to 0 ℃ and add organic amine or pyridine compounds and their as acid binding agent, perhaps will react the acid tail gas of the hydrogen halide that generates and import the alkali lye absorption;
Then, in above-mentioned solution, add halogen acyl halide, treat that halogen acyl halide dropwises the back and keep to stir and to make it to react completely, leave standstill, the solids removed by filtration insolubles, and with the distillation of the anhydrous aromatic hydrocarbon in filtrate recovery, obtain the ATRP reagent crude product based on the lower molecular weight carbon dioxide copolymer;
To be dissolved in dichloromethane solvent based on the ATRP reagent crude product of lower molecular weight carbon dioxide copolymer, be made into 3～60w
tThe solution of % respectively washs 2～3 times collected organic layer then successively with saturated ammonium chloride solution, saturated sodium bicarbonate solution and water;
Organic layer dewaters dry and after distillation removed methylene dichloride, products therefrom namely was based on the ATRP reagent of lower molecular weight carbon dioxide copolymer.
5. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 4, it is characterized in that: described lower molecular weight carbon dioxide copolymer has the terminal alcohol hydroxyl, and its molecular structural formula is at least a kind of in the following molecular structural formula:
Wherein: x, the integer of x1 〉=1; M and n can not be 0 integer simultaneously; M1 and n1 can not be 0 integer simultaneously; y
1, y
2, p, p1, q, the integer of q1 〉=0; R=H, CH
3, or phenyl.
6. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 5, it is characterized in that: the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～30000.
7. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 6, it is characterized in that: the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 300～18000.
8. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 4 is characterized in that: described aromatic hydrocarbon is at least a in dimethylbenzene, o-Xylol, p-Xylol, m-xylene, toluene, the benzene.
9. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 4 is characterized in that: described organic amine is at least a in triethylamine, three n-propyl amine, tri-n-butyl amine, the three positive decyl amine.
10. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 4 is characterized in that: described pyridine compounds and their is 2-methoxypyridine, 2-methylamino pyridine, 3-picoline, 3-amido pyridine, 3-pyridone, 3-phenylpyridine, pyridine, at least a in Dimethylamino pyridine, 4-picoline, the 4-tert .-butylpyridine.
11. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 4, it is characterized in that: described halogen acyl halide is 2-bromo-2-methyl-prop acyl chlorides, 2-bromo-2-methyl-prop acylbromide, 2-chloro-2-methyl-prop acylbromide, 2-chloro-2-methyl-prop acyl chlorides, chloro-acetyl chloride, the chloro acetyl bromide, bromo acetyl bromide, the bromo Acetyl Chloride 98Min., 2 bromo propionyl bromide, the 2-bromo propionyl chloro, 2-chlorine propionyl bromide, the 2-chlorpromazine chloride, the 3-bromopropionyl bromide, the 3-bromo propionyl chloro, the 3-chlorpromazine chloride, 3-chlorine propionyl bromide, 4-bromine butyryl bromide, the 4-bromobutanoylchloride, 4-neoprene acylbromide, the 4-chlorobutanoylchloride, 5-bromine bromine pivaloyl, 5-chlorine valeryl chloride, 5-bromine valeryl chloride, 5-chlorine bromine pivaloyl, Chloropivaloyl chloride, chloro pivaloyl bromine, the bromo pivaloyl chloride, the bromo pivaloyl chloride, 6-bromine hexanoyl bromide, 6-bromine caproyl chloride, 6-chlorine hexanoyl bromide, at least a in the 6-chlorine caproyl chloride.
12. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 11 is characterized in that: described halogen acyl halide is at least a in 2-bromo-2-methyl-prop acylbromide, 2-bromo-2-methyl-prop acyl chlorides, 2-chloro-2-methyl-prop acyl chlorides, 2-chloro-2-methyl-prop acylbromide, 2 bromo propionyl bromide, 2-bromo propionyl chloro, 2-chlorpromazine chloride, 2-chlorine propionyl bromide, chloro-acetyl chloride, chloro acetyl bromide, bromo acetyl bromide, the bromo Acetyl Chloride 98Min..
13. the preparation method of a kind of ATRP reagent based on the lower molecular weight carbon dioxide copolymer according to claim 4 is characterized in that: the amount of substance of described lower molecular weight carbon dioxide copolymer and halogen acyl halide and organic amine or pyridine compounds and their is such as down:
Lower molecular weight carbon dioxide copolymer: halogen acyl halide: organic amine or pyridine compounds and their=1: 1～3: 0～3.2.
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| CN103772689A (en) * | 2014-01-08 | 2014-05-07 | 华侨大学 | Low-molecular weight carbon dioxide copolymer combining Click reaction with ATRP (Atom Transfer Radical Polymerization) reaction and preparation method thereof |
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| CN101220534A (en) * | 2007-01-08 | 2008-07-16 | 吉林金源北方科技发展有限公司 | Full-biological degradation nonwoven cloth material |
| CN101983944A (en) * | 2010-07-07 | 2011-03-09 | 华侨大学 | Polycarboxylic acids water reducing agent containing low molecular weight carbon dioxide copolymer, and preparation method thereof |
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| CN101220534A (en) * | 2007-01-08 | 2008-07-16 | 吉林金源北方科技发展有限公司 | Full-biological degradation nonwoven cloth material |
| CN101983944A (en) * | 2010-07-07 | 2011-03-09 | 华侨大学 | Polycarboxylic acids water reducing agent containing low molecular weight carbon dioxide copolymer, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772689A (en) * | 2014-01-08 | 2014-05-07 | 华侨大学 | Low-molecular weight carbon dioxide copolymer combining Click reaction with ATRP (Atom Transfer Radical Polymerization) reaction and preparation method thereof |
| CN103772689B (en) * | 2014-01-08 | 2016-03-30 | 华侨大学 | Combine lower molecular weight carbon dioxide copolymer of Click reaction and ATRP reaction and preparation method thereof |
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