CN102746515A - Method for preparing block copolymers - Google Patents
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Abstract
The invention discloses a method for preparing block copolymers. The method includes adding one mole of double-bond compound, one mole of alpha-bromo polymer PA-Br, one mole of alpha-bromo polymer PB-Br, 2-10 moles of copper powder and 1-10 moles of polyamine into a reactor under the condition of existence of solvent, stirring, deoxygenizing, reacting for 24 hours at the temperature of 25-65 DEG C, and obtaining the block copolymers PA-b-PB. The method is simple in synthesis conditions, sources of the double-bond compound are convenient to obtain (1, 1-diphenylethlene and thiomicoler's ketone serving as commercialized reagent). The alpha-bromo polymer can be directly used after being synthesized through ATRP (atom transfer radical polymerization), posterior functionalization is omitted, and few synthesis steps are required. Besides, various kinds of polymers can be selected, reaction efficiency is high, conversion ratio of the block copolymers obtain can be up to 90%, and the method for preparing the block copolymers is a new convenient and high-efficiency copolymer synthesis method.
Description
Technical field
The present invention relates to the preparation method of polymkeric substance, relate in particular to a kind of preparation method of segmented copolymer.
Background technology
Current, along with the development of activity/controllable polymerization, the segmented copolymer that can obtain different structure and contain different functional groups through the different monomer polymerization of continuous initiation.Simultaneously, utilize combination between the various polymerization method can synthesize the segmented copolymer of different structure.But this segmented copolymer that obtains through the polymerization of continuous initiation different monomers is difficult to its each block is characterized.In order to overcome this problem, can synthesize the polymkeric substance that has different end groups earlier, utilize the reaction between the end group that two polymkeric substance are linked, obtain segmented copolymer.The advantage of this method is and can before reaction, each block be characterized clear (like molecular weight and MWD).But, utilize the prerequisite of two kinds of polymer terminal group prepared in reaction segmented copolymers to be, reaction has very high efficient, can obtain the segmented copolymer of high conversion.
(Chemical Communications, 2005,57 – 59) such as Jan C.M.van Hest had reported a kind of segmented copolymer synthetic novel method in 2005.They utilize the bromide that contains triple bond functional group as initiator, are triple-linked polymkeric substance (like PMMA, PS etc.) through the synthetic end group of atomic radical transfer polymerization reaction (ATRP); On the other hand, through the end group polymkeric substance that to modify synthetic end group be azido group (like PS-N
3And PEG-N
3).Utilize the click chemistry reaction of triple bond and azido group, obtain different types of segmented copolymer.But this method is functionalized after need the functional end-group to polymkeric substance, and the reactions step more complicated is unfavorable for carrying out scale operation.
The free radical coupling reaction can be used for the polymkeric substance (Progress in Polymer Science, 2012,37,1004 – 1030) of synthetic different structure.The direct coupling under the effect of Cu/ part of alpha-brominated polymkeric substance can only obtain symmetric bi-block copolymer.(e-polymer such as Yusuf Yagci; 2006; No50) reported coupled reaction between the different alpha-brominated things, the amount of their ratio, copper, cuprous bromide and the part through regulating two kinds of alpha-brominated things etc., the highest 56% the cross coupling rate that can only reach; Chief reason is that the free radical coupling reaction does not have selectivity, two kinds of different macromolecular radical (P
AAnd P
B) coupled reaction takes place can produce three kinds of polymkeric substance, i.e. P
A-P
A, P
A-P
BAnd P
B-P
B.Therefore, two kinds of different alpha-brominated polymkeric substance can't be obtained the segmented copolymer (P of high conversion through the method for direct coupling
A-P
B).
Free radical addition-coupled reaction is a kind of reaction efficiently, and bromide produces radical under copper/part effect, with free radical scavenger (double bond compound) addition reaction takes place; Original position generates stabilized radical; This stabilized radical and another molecule radical generation coupled reaction can be used for synthetic multi-block polymer (Journal ofPolymer Science:Part A:Polymer Chemistry, 2011 subsequently; 49,612-618; 2012,50,20292036) and regular polymkeric substance (Macromolecular Rapid Communications, 2011,32,15 of sequence; Macromolecules, 2011,44,8739).Utilize the addition rate constant of different macromolecular radicals and free radical scavenger (double bond compound) and the coupling rate constant is different can synthetic segmented copolymer.Therefore, can be through introducing suitable double bond compound as free radical scavenger, under copper/part effect, the alpha-brominated polymkeric substance generation free radical addition-coupled reaction different with two kinds obtains the segmented copolymer of high conversion.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method of segmented copolymer is provided.
The preparation method of segmented copolymer is under the condition that solvent exists, with 1 mole of double bond compound, 1 mole of alpha-brominated polymer P
A-Br, 1 mole of alpha-brominated polymer P
B-Br, 2～10 moles copper powder and 1～10 mole polyamine add in the reactor drum, stir, and after the deoxidation, 25～65 ℃ were reacted 24 hours, and obtained segmented copolymer P
A-b-P
B
Described segmented copolymer P
A-b-P
BMolecular structural formula be:
Wherein ,-X-does
R
1Be Wasserstoffatoms or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl, R
3Be phenyl, cyanic acid, the tertiary butyl or 4-(dimethylamino) phenyl.
Described alpha-brominated polymer P
AThe molecular structural formula of-Br is:
Wherein, R
1Be Wasserstoffatoms or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl.
Described alpha-brominated polymer P
BThe molecular structural formula of-Br is:
Wherein, R
1Be Wasserstoffatoms or methyl.
The molecular structural formula of described double bond compound is:
Wherein, R
1Be Wasserstoffatoms or methyl, R
3Be phenyl, cyanic acid, the tertiary butyl or 4-(dimethylamino) phenyl.
Described polyamine is 2,2 '-dipyridyl, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl, N, N; N ', N ", N "-pentamethyl-diethyl triamine, 1,1; 4,7,10,10-hexamethyl triethyl tetramine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
Synthesis condition of the present invention is simple, double bond compound convenient sources (is commercialization reagent like 1 and thiomicoler's ketone); Alpha-brominated polymkeric substance can be through the directly use of the synthetic back of ATRP, and it is functionalized not need to carry out the back again, and synthesis step is few; Available type of polymer is many; Reaction efficiency is high, the segmented copolymer transformation efficiency that obtains>90%, be a kind of convenience, segmented copolymer new synthetic method efficiently.
Description of drawings
The segmented copolymer PtBA-b-PS nuclear magnetic spectrogram that Fig. 1 obtains for embodiment 1;
Fig. 2 is raw material PEG-Br among the embodiment 2, the GPC spectrogram of PS-Br and segmented copolymer PEG-b-PS;
Fig. 3 is raw material PMA-Br among the embodiment 3, the GPC spectrogram of PS-Br and segmented copolymer PMA-b-PS.
Embodiment
Different alpha-brominated polymkeric substance is under copper/part effect; With double bond compound generation free radical addition-coupled reaction; Because different macromolecular radicals are different with the addition rate constant and the coupling rate constant of free radical scavenger (double bond compound); Can obtain segmented copolymer (is example with the 1).The preparing method's of segmented copolymer reaction formula does
The preparation method of segmented copolymer is under the condition that solvent exists, with 1 mole of double bond compound, 1 mole of alpha-brominated polymer P
A-Br, 1 mole of alpha-brominated polymer P
B-Br, 2～10 moles copper powder and 1～10 mole polyamine add in the reactor drum, stir, and after the deoxidation, 25～65 ℃ were reacted 24 hours, and obtained segmented copolymer P
A-b-P
B
Described segmented copolymer P
A-b-P
BMolecular structural formula be:
Wherein ,-X-does
R
1Be Wasserstoffatoms or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl, R
3Be phenyl, cyanic acid, the tertiary butyl or 4-(dimethylamino) phenyl.
Described alpha-brominated polymer P
AThe molecular structural formula of-Br is:
Wherein, R
1Be Wasserstoffatoms or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl.
Described alpha-brominated polymer P
BThe molecular structural formula of-Br is:
Wherein, R
1Be Wasserstoffatoms or methyl.
The molecular structural formula of described double bond compound is:
Wherein, R
1Be Wasserstoffatoms or methyl, R
3Be phenyl, cyanic acid, the tertiary butyl or 4-(dimethylamino) phenyl.
Described polyamine is 2,2 '-dipyridyl, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl, N, N; N ', N ", N "-pentamethyl-diethyl triamine, 1,1; 4,7,10,10-hexamethyl triethyl tetramine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
The present invention explains with following embodiment, but scope of the present invention is not limited to these embodiment.
All polymeric reaction conditions carry out under the anhydrous reaction conditions of anaerobic.
The double bond compound molecular formula that is used for embodiment is as follows:
Embodiment 1 dithiobenzoic acid ethyl ester (EDTB) is as double bond compound synthetic segmented copolymer PtBA-b-PS
(1) through the synthetic alpha-brominated PS (PS-Br) of ATRP (ATRP) method: with 19.5mg cuprous bromide (1.36 * 10
-4Mol) add in the polymerizing pipe nitrogen replacement five times.Add the 186 μ L α-bromine ethylbenzene (1.36 * 10 that outgased
-3Mol), 28.4 μ L N, N, N ', N ", N "-pentamethyl-diethyl triamine (1.36 * 10
-4Mol) and 3mL (2.73 * 10
-2Mol) vinylbenzene, 100 ℃ were reacted 4 hours.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=1100g/mol, molecular weight distributing index (PDI)=1.10.
(2) through the synthetic alpha-brominated ROHM tert-butyl ester (PtBA-Br) of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [tBA]
0: [2-EBP]
0: [CuBr]
0: [PMDETA]
0=70:1:1:1,25% acetone soln, 60 ℃ were reacted 3 hours.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=2700g/mol, molecular weight distributing index (PDI)=1.14.
(3) segmented copolymer PtBA-b-PS is synthetic: with the alpha-brominated PS PS-Br of 110mg, and the alpha-brominated ROHM tert-butyl ester of 280mg PtBA-Br, 18mg dithiobenzoic acid ethyl ester (EDTB); 416 μ LN, N, N '; N "; N "-pentamethyl-diethyl triamine (PMDETA), 2mL THF add in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Nitrogen adds the 14mg copper powder down.Reacted 24 hours down at 25 ℃.Product is diluted with THF, cross the post copper removal, concentrate 50 ℃ of drying under vacuum overnight through neutral alumina.Resulting polymers is through gel permeation chromatography (GPC) test, M
n=3800g/mol, PDI=1.20.
Embodiment 21, and 1-diphenylethlene (DPE) is as double bond compound synthetic segmented copolymer PEG-b-PS
(1) alpha-brominated poly glycol monomethyl ether (PEG-Br) is synthetic: with 7.5g PEG-OH (M
n=750g/mol, commercially available) be dissolved in the dry toluene of crossing, vacuum-drying, azeotropic water removing repeats twice, obtains anhydrous PEG-OH.Add the 1mL pyridine, 20mL exsiccant CH
2Cl
2Ice bath slowly drips the CH that contains the 2mL2-bromopropionyl bromide down
2Cl
2Solution 20mL.Dropwise in half a hour.Slowly rise to room temperature, stirred overnight.Remove by filter the white particle deposition.Solution is used 3 * 15mL1M HCl aqueous solution, 3 * 15mL5%NaHCO respectively
3The aqueous solution, 3 * 15mL deionized water, the saturated NaCl solution washing of 15mL, organic layer merge the back and use anhydrous MgSO
4Dry.Filter, concentrate, product is dissolved in the 20mL ether, slowly drip normal hexane to solution again and muddiness occurs, solution is positioned in the refrigerating chamber, white solid is separated out.Filter, vacuum-drying obtains little yellow solid.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=1070g/mol, molecular weight distributing index (PDI)=1.07.
(2) through the synthetic alpha-brominated PS (PS-Br) of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [vinylbenzene]
0: [2 bromopropionic acid ethyl ester]
0: [CuBr]
0: [PMDETA]
0=70:1:1:1,100 ℃ were reacted 2 hours.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=2800g/mol, molecular weight distributing index (PDI)=1.10.
(3) segmented copolymer PEG-b-PS is synthetic: with the alpha-brominated PS PS-Br of 280mg, and the alpha-brominated poly glycol monomethyl ether PEG-Br of 107mg, 18mg1; 1-diphenylethlene (DPE), 41.6 μ L N, N; N ', N ", N "-pentamethyl-diethyl triamine PMDETA; The 2mL THF adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Nitrogen adds the 140mg copper powder down.Reacted 24 hours down at 65 ℃.Product is diluted with THF, cross the post copper removal, concentrate 50 ℃ of drying under vacuum overnight through neutral alumina.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=3870g/mol, molecular weight distributing index (PDI)=1.23.
Embodiment 31, and 1-diphenylethlene (DPE) is as double bond compound synthetic segmented copolymer PMA-b-PS
(1) through the synthetic alpha-brominated polymethyl acrylate (PMA-Br) of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [methyl acrylate]
0: [2-EBP]
0: [CuBr]
0: [PMDETA]
0=40:1:1:1,60 ℃ were reacted 0.5 hour.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=1200g/mol, molecular weight distributing index (PDI)=1.18.
(2) through the synthetic alpha-brominated PS (PS-Br) of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [vinylbenzene]
0: [2 bromopropionic acid ethyl ester]
0: [CuBr]
0: [PMDETA]
0=70:1:1:1,100 ℃ were reacted 2 hours.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=2800g/mol, molecular weight distributing index (PDI)=1.13.
(3) segmented copolymer PMA-b-PS is synthetic: with the alpha-brominated PS PS-Br of 280mg, and the alpha-brominated polymethyl acrylate PMA-Br of 120mg, 18mg1; 1-diphenylethlene (DPE), 41.6 μ LN, N; N ', N ", N "-pentamethyl-diethyl triamine PMDETA; The 2mL THF adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Nitrogen adds the 14mg copper powder down.Reacted 24 hours down at 45 ℃.Product is diluted with THF, cross the post copper removal, concentrate 50 ℃ of drying under vacuum overnight through neutral alumina.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=4050g/mol, molecular weight distributing index (PDI)=1.23.
Embodiment 41, and 1-diphenylethlene (DPE) is as double bond compound synthetic segmented copolymer PMA-b-PS
(1) through the synthetic alpha-brominated polymethyl acrylate (PMA-Br) of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [methyl acrylate]
0: [2-EBP]
0: [CuBr]
0: [PMDETA]
0=80:1:1:1,90 ℃ were reacted 18 minutes.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=4000g/mol, molecular weight distributing index (PDI)=1.14.
(2) through the synthetic alpha-brominated PS (PS-Br) of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [vinylbenzene]
0: [2 bromopropionic acid ethyl ester]
0: [CuBr]
0: [PMDETA]
0=20:1:0.1:0.1,100 ℃ were reacted 1 hour.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=760g/mol, molecular weight distributing index (PDI)=1.10.
(3) segmented copolymer PMA-b-PS is synthetic: with the alpha-brominated PS PS-Br of 76mg, and the alpha-brominated polymethyl acrylate PMA-Br of 400mg, 18mg1; 1-diphenylethlene (DPE), 41.6 μ LN, N; N ', N ", N "-pentamethyl-diethyl triamine PMDETA; The 2mL THF adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Nitrogen adds the 14mg copper powder down.Reacted 24 hours down at 45 ℃.Product is diluted with THF, cross the post copper removal, concentrate 50 ℃ of drying under vacuum overnight through neutral alumina.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=4500g/mol, molecular weight distributing index (PDI)=1.28.
Embodiment 51, and 1-diphenylethlene (DPE) is as double bond compound synthetic segmented copolymer PMA-b-PS
(1) through the synthetic alpha-brominated polymethyl acrylate (PMA-Br) of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [methyl acrylate]
0: [2-EBP]
0: [CuBr]
0: [PMDETA]
0=40:1:1:1,60 ℃ were reacted 0.5 hour.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=1200g/mol, molecular weight distributing index (PDI)=1.18.
(2) through the synthetic alpha-brominated PS (PS-Br) of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [vinylbenzene]
0: [2 bromopropionic acid ethyl ester]
0: [CuBr]
0: [PMDETA]
0=100:1:1:1,100 ℃ were reacted 4 hours.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=4600g/mol, molecular weight distributing index (PDI)=1.14.
(3) segmented copolymer PMA-b-PS is synthetic: with the alpha-brominated PS PS-Br of 460mg, and the alpha-brominated polymethyl acrylate PMA-Br of 120mg, 18mg1; 1-diphenylethlene (DPE), 41.6 μ LN, N; N ', N ", N "-pentamethyl-diethyl triamine PMDETA; The 2mL THF adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Nitrogen adds the 14mg copper powder down.Reacted 24 hours down at 45 ℃.Product is diluted with THF, cross the post copper removal, concentrate 50 ℃ of drying under vacuum overnight through neutral alumina.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=5830g/mol, molecular weight distributing index (PDI)=1.29.
Table 1 be among the embodiment 3-5 with 1 (DPE) as double bond compound synthetic segmented copolymer PMA-b-PS
Embodiment 61, and 1-diphenylethlene (DPE) is as double bond compound synthetic segmented copolymer PMMA-b-PS
(1) through the synthetic alpha-brominated polymethylmethacrylate (PMMA-Br) of ATRP (ATRP) method: with 2-isobutyl ethyl bromide (2-EBiB) as initiator, [TEB 3K]
0: [2-EBiB]
0: [CuBr]
0: [PMDETA]
0=80:1:1:1, methyl-phenoxide are as solvent, and 60 ℃ were reacted 2 hours.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=4000g/mol, molecular weight distributing index (PDI)=1.25.
(2) segmented copolymer PMMA-b-PS is synthetic: with the alpha-brominated PS PS-Br of 280mg (M
n=2800g/mol), and the alpha-brominated polymetylmethacrylate-Br of 400mg, 18mg1,1-diphenylethlene (DPE), 50mg2,2 '-dipyridyl, 2mL THF add in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Nitrogen adds the 14mg copper powder down.Reacted 24 hours down at 45 ℃.Product is diluted with THF, cross the post copper removal, concentrate 50 ℃ of drying under vacuum overnight through neutral alumina.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=6100g/mol, molecular weight distributing index (PDI)=1.38.
Embodiment 7 dithiobenzoic acid ethyl esters (EDTB) are as double bond compound synthetic segmented copolymer PCL-b-PMS
(1) alpha-brominated polycaprolactone (PCL-Br) is synthetic: with 10g PEG-OH (M
n=2000g/mol, commercially available), 1mL pyridine, 20mL exsiccant CH
2Cl
2Ice bath slowly drips the CH that contains 2mL2-bromo isobutyl acylbromide down
2Cl
2Solution 20mL.Slowly rise to room temperature, stirred overnight.Filter, filtrating is used the 1M HCl aqueous solution, 5%NaHCO respectively
3The aqueous solution, deionized water and saturated NaCl solution washing, organic layer merge the back and use anhydrous MgSO
4Dry.Filter, concentrate, precipitate in the normal hexane.Filter, vacuum-drying obtains little yellow solid.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=2100g/mol, molecular weight distributing index (PDI)=1.05.
(2) through the synthetic alpha-brominated p-methylstyrene (PMS-Br) that gathers of ATRP (ATRP) method: with 2 bromopropionic acid ethyl ester (2-EBP) as initiator, [p-methylstyrene]
0: [2 bromopropionic acid ethyl ester]
0: [CuBr]
0: [PMDETA]
0=100:1:1:1,100 ℃ were reacted 2 hours.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=4600g/mol, molecular weight distributing index (PDI)=1.11.
(3) segmented copolymer PCL-b-PMS is synthetic: with the alpha-brominated p-methylstyrene PMS-Br that gathers of 230mg, the alpha-brominated polycaprolactone of 105mg (PCL-Br), 9mg dithiobenzoic acid ethyl ester (EDTB); 20.8 μ LN, N, N '; N "; N "-pentamethyl-diethyl triamine PMDETA, 2mL THF add in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Nitrogen adds the 7.1mg copper powder down.Reacted 24 hours down at 25 ℃.Product is diluted with THF, cross the post copper removal, concentrate 50 ℃ of drying under vacuum overnight through neutral alumina.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=7100g/mol, molecular weight distributing index (PDI)=1.32.
Embodiment 8 thiomicoler's ketones (TMK) are as double bond compound synthetic segmented copolymer PEG-b-PS
(1) alpha-brominated poly glycol monomethyl ether (PEG-Br) is synthetic: shown in the embodiment 2 (1).
(2) through shown in synthetic alpha-brominated PS (PS-Br): the embodiment 5 (2) of ATRP (ATRP) method.
(3) segmented copolymer PEG-b-PS is synthetic: with the alpha-brominated PS PS-Br of 460mg; The alpha-brominated poly glycol monomethyl ether PEG-Br of 107mg; 28.4mg thiomicoler's ketone (TMK); 30 μ L three [2-(dimethylin) ethyl] amine, 2mL THF add in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Nitrogen adds the 28mg copper powder down.Reacted 24 hours down at 35 ℃.Product is diluted with THF, cross the post copper removal, concentrate 50 ℃ of drying under vacuum overnight through neutral alumina.Resulting polymers is through gel permeation chromatography (GPC) test, number-average molecular weight (M
n)=5870g/mol, molecular weight distributing index (PDI)=1.25.
Claims (6)
1. the preparation method of a segmented copolymer is characterized in that under the condition that solvent exists, with 1 mole of double bond compound, 1 mole of alpha-brominated polymer P
A-Br, 1 mole of alpha-brominated polymer P
B-Br, 2～10 moles copper powder and 1～10 mole polyamine add in the reactor drum, stir, and after the deoxidation, 25～65 ℃ were reacted 24 hours, and obtained segmented copolymer P
A-b-P
B
2. the preparation method of a kind of segmented copolymer according to claim 1 is characterized in that described segmented copolymer P
A-b-P
BContain link unit-X-, molecular structural formula is:
Wherein ,-X-does
R
1Be Wasserstoffatoms or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl, R
3Be phenyl, cyanic acid, the tertiary butyl or 4-(dimethylamino) phenyl.
3. the preparation method of a kind of segmented copolymer according to claim 1 is characterized in that described alpha-brominated polymer P
AThe molecular structural formula of-Br is:
Wherein, R
1Be Wasserstoffatoms or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl.
4. the preparation method of a kind of segmented copolymer according to claim 1 is characterized in that described alpha-brominated polymer P
BThe molecular structural formula of-Br is:
Wherein, R
1Be Wasserstoffatoms or methyl.
5. the preparation method of a kind of segmented copolymer according to claim 1 is characterized in that described double bond compound molecular structural formula is:
Wherein, R
1Be Wasserstoffatoms or methyl, R
3Be phenyl, cyanic acid, the tertiary butyl or 4-(dimethylamino) phenyl.
6. the preparation method of a kind of segmented copolymer according to claim 1 is characterized in that described polyamine is: 2, and 2 '-dipyridyl, 4,4 '-two (5-nonyls)-2; 2 '-dipyridyl, N, N, N ', N "; N "-pentamethyl-diethyl triamine, 1,1,4; 7,10,10-hexamethyl triethyl tetramine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
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Cited By (2)
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|---|---|---|---|---|
| JP2016508488A (en) * | 2013-02-06 | 2016-03-22 | ジ・オーストラリアン・ナショナル・ユニバーシティー | Radical orbit switching |
| CN105461904A (en) * | 2015-11-27 | 2016-04-06 | 浙江大学 | Novel method for preparing polymer on basis of carbon free radical coupling reaction |
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| CN101585921A (en) * | 2009-06-18 | 2009-11-25 | 天津大学 | Temperature-sensitive polyethylenimine-graft-poly(diethyleneglycol methyl ether methacrylate-b-hydroxyethyl methacrylate) block copolymer, preparing method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101585921A (en) * | 2009-06-18 | 2009-11-25 | 天津大学 | Temperature-sensitive polyethylenimine-graft-poly(diethyleneglycol methyl ether methacrylate-b-hydroxyethyl methacrylate) block copolymer, preparing method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016508488A (en) * | 2013-02-06 | 2016-03-22 | ジ・オーストラリアン・ナショナル・ユニバーシティー | Radical orbit switching |
| CN105461904A (en) * | 2015-11-27 | 2016-04-06 | 浙江大学 | Novel method for preparing polymer on basis of carbon free radical coupling reaction |
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