CN102010490B - Method for preparing degradable multiblock polymer - Google Patents
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Abstract
The invention discloses a method for preparing a degradable multiblock polymer, which comprises the following steps of: adding 1mol of polymer with the terminal functional group of halogen, 0.5-5mol of radical capture agent, 2-10mol of metal copper or copper salt and 2-10mol of polyamine into a reactor under the condition of the existence of a solvent; and after stirring and deoxidizing, reacting at 10-100 DEG C for 0.1-24 hours to obtain the degradable multiblock polymer. The invention has the advantages of simple synthesizing method and mild reaction condition and can be used for synthesizing multiblock polymers with different monomer types and block number, and the block number can exceed 30 blocks. The degradable multiblock polymer can be also prepared by reacting the polymer with a main chain of different monomers and the terminal functional group of halogen with the radical capture agent. When the multiblock polymer is heated to certain temperature, the multiblock polymer can be degraded to obtain a monodispersed low-molecular weight oligomer.
Description
Technical field
The present invention relates to the preparation method of polymkeric substance, relate in particular to a kind of preparation method of degradable multiblock polymer.
Background technology
Multi-block polymer is formed by different polymer segment links, according to the polymkeric substance difference of link, can show different performances.For example, soft chain segment and hard segment are linked, light-water links with hydrophobic segment or crystallization links with noncrystalline segment, and the material of the segmented copolymer obtaining just can show some unconventional performance or forms.Can be for the exploitation of the expanding material of novel surfactant, thermoplastic elastomer and polymer blending.
Traditional segmented copolymer synthetic method mainly contains two kinds.The first is constantly to add new different monomers in active polymerization system, and polymkeric substance is prepared on a section ground, can be referred to as method piecemeal.The second is first to synthesize the oligopolymer with different functional end-groups, then between oligopolymer, by the reaction between functional group, makes its bonding form segmented copolymer, can be referred to as coupling method.In above-mentioned two kinds of methods, first method need to be added new monomer through multistep, carries out polyreaction.The introducing of new monomer unavoidably can be introduced impurity and make active centre inactivation, produces the polymkeric substance lower than expection block number.On the other hand, owing to being the strategy synthesizing piecemeal, the synthetic block number obtaining of the method can not be very high.The synthetic block number of second method depends on the level of response of end group, when end group level of response is not high, is difficult to obtain the polymkeric substance of high block number.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of degradable multiblock polymer is provided.
The preparation method of degradable multiblock polymer is under the condition existing at solvent, the polyamines of the polymkeric substance that is halogen by 1 mole of terminal functionality and 0.5～5 mole of free radical scavenger, the metallic copper of 2～10 moles or mantoquita and 2～10 moles adds in reactor, stir, after deoxidation, 10～100 ℃ are reacted 0.1～24 hour, obtain degradable multiblock polymer.
2. the preparation method of a kind of degradable multiblock polymer according to claim 1, it is characterized in that described free radical scavenger is the nitroso compound shown in following formula (A1), diphenyl ethene compounds (A2) or thione compounds (A3):
Wherein, R
1, R
3for hydrogen, methyl, ethyl, sec.-propyl, tertiary butyl, aromatic base, cyano group; R
2for hydrogen, tertiary butyl, aromatic base, cyano group, methoxyl group.
Described metallic copper is copper powder, copper wire or copper sheet.Described mantoquita is: Red copper oxide, cuprous sulfide, cuprous telluride, selenkupfer, cuprous bromide, cuprous chloride or cuprous iodide.
Described polyamines is 2, 2 '-dipyridyl, 4, 4 '-bis-(5-nonyls)-2, 2 '-dipyridyl, 1, 10-phenanthroline, N, N, N ', N '-Tetramethyl Ethylene Diamine, N-propyl group-(2-pyridyl) methylamine, 2, 2 ': 6 ', 2 "-terpyridyl, 4, 4 ', 4 "-tri-(5-nonyls)-2, 2 ': 6 ', 2 "-terpyridyl, N, N, N ', N ", N "-pentamethyl-diethyl triamine, N, N-bis-(2-pyridylmethyl) octylame, 1, 1, 4, 7, 10, 10-hexamethyl trientine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
Described end group is that the polymkeric substance of halogen is: α-brominated Polystyrene, α, ω-brominated Polystyrene, α-bromination polyacrylic acid tert-butyl ester, α, ω-bromination polyacrylic acid tert-butyl ester, α, ω-bromination polycaprolactone, α, ω-brominated Polystyrene-b-polyacrylic acid tert-butyl ester, α, ω-bromination polyethylene oxide-b-poly(propylene oxide) or α, ω-brominated Polystyrene-b-polypropylene.
The present invention, by using the polymkeric substance that terminal functionality is halogen, reacts with free radical scavenger, prepares many segmented degradable polymers.The polymkeric substance that contains end group halogen used, can be polystyrene type, polyacrylate(s), and polymethacrylate, polyethers, polylactone class, polyamide-based, polyolefins, polypeptide, protein etc.As long as its end group contains halogen atom, can react with metal or metallic salt and produce free radical, all applicable to present method.
It is the polymkeric substance of halogen that the present invention adopts terminal functionality, by reacting with metal or metallic salt, generates living radical, reacts and obtains degradable multiblock polymer with free radical scavenger.The end group level of response of the method can approach 100%, obtains the large (M of molecular weight
n> 200000g/mol), the polymkeric substance of high block number.When being heated to certain temperature, the degraded that this multi-block polymer can occur, obtains monodispersed low-molecular-weight oligomer.The present invention can also use the polymkeric substance that main chain is halogen for different monomers, terminal functionality, reacts prepare degradable segmented copolymer with free radical scavenger.According to aforesaid method, there are two kinds of approach can obtain degradable segmented copolymer.The one, use segmented copolymer that main chain contains halogen functional group for end group as reactant, react with free radical scavenger, obtain the degradable segmented copolymer of different molecular weight under certain condition; Another kind method is to use polymkeric substance that two or more main chain contains halogen functional group for different monomers both-end as reactant, reacts with free radical scavenger, obtains the degradable segmented copolymer of different molecular weight under certain condition.
Embodiment
The present invention illustrates by the following examples, but scope of the present invention is not limited to these embodiment.
All polymeric reaction conditions are to carry out under the reaction conditions of anaerobic.
Free radical scavenger molecular formula for embodiment is as follows:
The synthetic two block polystyrene of embodiment 1 use 2-methyl-2-nitroso-group propane (MNP) reaction
By atom transfer radical polymerization (ATRP) method (Journal of Polymer Science:Part A:Polymer Chemistry, 2000,38,2274-2283) synthetic α-brominated Polystyrene (PS-Br): by 19.5mg cuprous bromide (1.36 × 10
-4mol) add in polymerizing pipe nitrogen replacement five times.Add 186 degassed μ L α-bromine ethylbenzene (1.36 × 10
-3mol), 28.4 μ L N, N, N ', N ", N " and-pentamethyl-diethyl triamine (PMDETA) (1.36 × 10
-4mol) and 3mL (2.73 × 10
-2mol) vinylbenzene, 100 ℃ are reacted 6 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=1110g/mol, molecular weight distributing index (PDI)=1.10.
Bi-block copolymer is synthetic: by 12.8mg copper powder (particle diameter=625 order, 2 × 10
-4mol), 112mg α-brominated Polystyrene PS-Br (1 × 10
-4mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 41 μ L N, N, N ', N ", N "-pentamethyl-diethyl triamine (PMDETA) (2 × 10
-4mol), 4.4mg MNP (5 × 10
-5mol) tetrahydrofuran solution.10 ℃ are reacted 6 hours.Polymkeric substance is dissolved in acetone, through neutral alumina, crosses post copper removal, concentrated, methanol extraction, and 50 ℃ of vacuum-dryings are spent the night.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=2240g/mol, PDI=1.10
The synthetic two block polypropylene tert-butyl acrylates of embodiment 2 use 2-methyl-2-nitroso-group propane (MNP) reaction
By ATRP, synthesize α-bromination polyacrylic acid tert-butyl ester PtBA-Br: using 2 bromopropionic acid ethyl ester (2-EBP) as initiator.[tBA]
0: [2-EBP]
0: [CuBr]
0: [PMDETA]
0=200: 1: 1: 1,25% acetone soln, 60 ℃ are reacted 3 hours.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=5200g/mol, PDI=1.18.
Bi-block copolymer is synthetic: by 12.8mg copper powder (particle diameter=100 order, 2 × 10
-4mol), 520mg α-bromination polymethyl acrylate PtBA-Br (1 × 10
-4mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 41 μ L PMDETA (2 × 10
-4mol), 4.4mg MNP (5 × 10
-5mol) THF solution.100 ℃ are reacted 0.1 hour.Polymkeric substance is dissolved in tetrahydrofuran (THF), through neutral alumina, crosses post copper removal, concentrated, methanol extraction, and 50 ℃ of vacuum-dryings are spent the night.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=10300g/mol, PDI=1.22
The synthetic many blocks polystyrene of 2-methyl-2-nitroso-group propane (MNP) reaction for embodiment 3-7
By ATRP, synthesize α, ω-brominated Polystyrene Br-PS-Br: with 2,5-dibromo diethylene adipate (DEDBA) as initiator.[St]
0: [DEDBA]
0: [CuBr]
0: [PMDETA]
0=20: 1: 0.2: 0.2,100 ℃ were reacted 80 minutes.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=1260g/mol, PDI=1.10.
Many blocks polystyrene is synthetic: by 14mg copper powder (particle diameter=625 order, 2.2 × 10
-4mol), 130mg α, ω-brominated Polystyrene Br-PS-Br (1 × 10
-4mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 41 μ L PMDETA (2 × 10
-4mol), 8.7mg MNP (1 × 10
-4mol) THF solution.Under room temperature, react different time, termination reaction.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, and concentrated, through benzene/methanol system precipitation fractionation purifying, 40 ℃ of vacuum-dryings are spent the night, yield 90%.
The molecular weight of the polymkeric substance of the prepared acquisition of embodiment 3-7 and block number are as shown in Table 1.
Table one
The synthetic many block polypropylenes tert-butyl acrylate of 2-methyl-2-nitroso-group propane (MNP) reaction for embodiment 8-10
By ATRP, synthesize α, ω-bromination polyacrylic acid tert-butyl ester Br-PtBA-Br, with 2,5-dibromo diethylene adipate (DEDBA) as initiator.[tBA]
0: [DEDBA]
0: [CuBr]
0: [PMDETA]
0=100: 1: 0.5: 0.5,25% acetone soln.60 ℃ are reacted 4 hours.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=5900g/mol, PDI=1.16.
Multi-block polymer is synthetic: by 12.8mg copper powder (particle diameter=625 order, 2 × 10
-4mol), 300mgBr-PtBA-Br (5 × 10
-5mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 20.8 μ L PMDETA (1 × 10
-4mol), 4.4mg MNP (5 × 10
-5mol) THF solution.Under room temperature, reaction different time, termination reaction.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, and concentrated, through acetone/methanol/aqueous systems precipitation fractionation purifying, polymkeric substance spends the night 40 ℃ of vacuum-dryings.
The molecular weight of the polymkeric substance of the prepared acquisition of embodiment 8-10 and block number are as shown in Table 2.
Table two
The synthetic many blocks polycaprolactone of embodiment 11 use 2-methyl-2-nitroso-group propane (MNP) reaction
α, synthesizing of ω-bromination polycaprolactone (Br-PCL-Br): by 4g α, alpha, omega-dihydroxy polycaprolactone (2000g/mol, 2mmol), 488mg Dimethylamino pyridine, 0.58mL triethylamine and 40mL methylene dichloride join in there-necked flask, dropwise add 0.5mL 2-bromine isobutyl acylbromide at 0 ℃.Under room temperature, stirring is spent the night, methanol extraction, 50 ℃ of vacuum-dryings.
Multi-block polymer is synthetic: by 32mg copper wire (diameter=1mm, 5 × 10
-4mol), 123mgBr-PCL-Br (5 × 10
-5mol, 2460g/mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 104 μ L PMDETA (5 × 10
-4mol), 22mg MNP (2.5 × 10
-4mol) THF solution.Under room temperature, react termination reaction 12 hours.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, and concentrated, precipitation fractionation purifying, obtains polymkeric substance, and polymkeric substance spends the night 40 ℃ of vacuum-dryings.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=13000g/mol, PDI=1.98, block number=5.
The synthetic polyacrylic acid tert-butyl ester-b-polystyrene-b-polyacrylic acid tert-butyl ester of embodiment 12 use 2-methyl-2-nitroso-group propane (MNP) reaction [(PtBA-b-PS-b-PtBA)
m] segmented copolymer
ATRP method is synthesized α, and ω-bromination is gathered the polyacrylic acid tert-butyl ester-b-vinylbenzene-b-polyacrylic acid tert-butyl ester (Br-PtBA-PS-PtBA-Br), take Br-PS-Br as polymerization initiator: [tBA]
0: [Br-PS-Br]
0: [CuBr]
0: [CuBr
2]
0: [PMDETA]
0=40: 1: 0.4: 0.02: 0.42,25% acetone soln, reacts 1 hour at 60 ℃.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=2780g/mol, PDI=1.18.
Multi-block polymer is synthetic: by 12.8mg copper powder (particle diameter=625 order, 2 × 10
-4mol), 139mg multipolymer Br-PtBA-PS-PtBA-Br (2780g/mol, 5 × 10
-5mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 41 μ L PMDETA (1 × 10
-4mol), the THF solution of 4.4mg MNP.Under room temperature, react termination reaction 8 hours.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, concentrated, benzene/methanol system precipitation fractionation purifying, and 40 ℃ of vacuum-dryings are spent the night, yield 85%.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=39000, PDI=1.99, block number=14.
Embodiment 13 use 2-methyl-2-nitroso-group propane (MNP) reaction synthetic polystyrene-b-polyacrylic acid tert-butyl ester-b-polystyrene [(PS-b-PtBA-b-PS)
m] segmented copolymer
ATRP method is synthesized α, and the ω-brominated Polystyrene-b-polyacrylic acid tert-butyl ester-b-polystyrene (Br-PS-PtBA-PS-Br), take Br-PtBA-Br as polymerization initiator: [St]
0: [Br-PtBA-Br]
0: [CuBr]
0: [PMDETA]
0=20: 1: 0.2: 0.2, react 1 hour at 100 ℃.M
n＝4320g/mol，PDI＝1.18。
Multi-block polymer is synthetic: by 12.8mg copper powder (particle diameter=100 order, 2 × 10
-4mol), 206mg multipolymer Br-PS-PtBA-PS-Br (4320g/mol, 5 × 10
-5mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 41 μ L PMDETA (1 × 10
-4mol), 4.4mg MNP (5 × 10
-5mol) toluene solution.Under room temperature, react termination reaction 2 hours.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, concentrated, benzene/methanol extraction grading purification, and 40 ℃ of vacuum-dryings are spent the night, yield 92%.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=70800, PDI=1.94, block number=16.
Synthetic polyethylene oxide-b-poly(propylene oxide) the segmented copolymer of embodiment 14 use 2-methyl-2-nitroso-group propane (MNP) reaction
α, synthesizing of ω-bromination polyethylene oxide-b-poly(propylene oxide)-b-polyethylene oxide (Br-PEO-b-PPO-b-PEO-Br): by 11.6g Pluronic P123 (5800g/mol, 2mmol), 488mg Dimethylamino pyridine, 0.58mL triethylamine and 40mL methylene dichloride join in there-necked flask, dropwise add 0.5mL 2-bromine isobutyl acylbromide at 0 ℃.Under room temperature, stirring is spent the night, normal hexane precipitation, 50 ℃ of vacuum-dryings.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=6260g/mol, PDI=1.25.
Multi-block polymer is synthetic: by 28.8mg Red copper oxide (2 × 10
-4mol), 313mgBr-PEO-b-PPO-b-PEO-Br (5 × 10
-5mol, 6260g/mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 23mg Me
6tREN (1 × 10
-4mol), 4.4mg MNP (5 × 10
-5mol) THF solution.Under room temperature, react termination reaction 6 hours.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, and concentrated, precipitation fractionation purifying, obtains polymkeric substance, and polymkeric substance spends the night 40 ℃ of vacuum-dryings.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=113900g/mol, PDI=2.18, block number=18.
Synthetic polypropylene-b-polystyrene the segmented copolymer of embodiment 15 use 2-methyl-2-nitroso-group propane (MNP) reaction
According to the method for bibliographical information (Macromolecules 2005,38,10373-10378) synthetic polymer initiator α, ω-bromination polypropylene.
α, alpha, omega-dihydroxy polypropylene is synthetic: by 10g α, ω-bis-(2-propenyl) polypropylene oligopolymer (1000g/mol) are dissolved in 200mL THF, dropwise add the THF solution 40mL of 1M borine, reacts 5 hours at 60 ℃.The NaOH aqueous solution and the methanol solution that add 5M, ice bath is cooling, drips 35%H
2o
2solution 50mL, reacts 6 hours methanol extraction, 50 ℃ of vacuum-dryings at 40 ℃.
Polymerization initiator α, ω-bromination polypropylene is synthetic: by 2g α, alpha, omega-dihydroxy polypropylene (1000g/mol, 2mmol), 488mg Dimethylamino pyridine, 0.58mL triethylamine and 40mL methylene dichloride join in there-necked flask, dropwise add 0.5mL 2-bromine isobutyl acylbromide at 0 ℃.Under room temperature, stirring is spent the night, methanol extraction, 50 ℃ of vacuum-dryings.
By ATRP, synthesize α, ω-brominated Polystyrene-b-polypropylene-b-polystyrene (Br-PS-PP-PS-Br): with α, ω-bromination polypropylene is as initiator: [St]
0: [Br-PP-Br]
0: [CuBr]
0: [PMDETA]
0=20: 1: 0.2: 0.2,100 ℃ were reacted 80 minutes.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=2200g/mol, PDI=1.25.
Multi-block polymer is synthetic: by 28.8mg Red copper oxide (2 × 10
-4mol), 110mgBr-PS-PP-PS-Br (5 × 10
-5mol, 2200g/mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 20.8 μ L PMDETA (1 × 10
-4mol), 4.4mg MNP (5 × 10
-5mol) THF solution.Under room temperature, react termination reaction 24 hours.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, and concentrated, precipitation fractionation purifying, obtains polymkeric substance, and polymkeric substance spends the night 40 ℃ of vacuum-dryings.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=31200g/mol, PDI=2.31, block number=14.
The synthetic many blocks polystyrene of embodiment 16 use thiomicoler's ketone (TMK) reaction
By 14mg copper powder (particle diameter=625 order, 2.2 × 10
-4mol), 120mg Br-PS-Br (5 × 10
-5mol, 1200g/mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 41 μ L PMDETA (1 × 10
-4mol), 28.4mg TMK (1 × 10
-4mol) THF solution.Under room temperature, react termination reaction 2 hours.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, concentrated, methanol extraction, 40 ℃ of vacuum-dryings.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=3210g/mol, PDI=1.72
The synthetic many blocks polystyrene of embodiment 17 use 1，1-diphenylethylene (DPE) reaction
By 14mg Cu powder (particle diameter=625 order, 2.2 × 10
-4mol), 120mg Br-PS-Br (1 × 10
-4mol) add in ampoul tube N
2replace five times.Add 1mL degassed containing 41 μ L PMDETA (2 × 10
-4mol), 17.7 μ L DPE (1 × 10
-4mol) toluene solution.Lower 2 hours of room temperature, termination reaction.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, concentrated, methanol extraction, and 40 ℃ of vacuum-dryings are spent the night.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=11000g/mol, PDI=2.51.
The synthetic many block polypropylenes tert-butyl acrylate of embodiment 18 use 1，1-diphenylethylene (DPE) reaction
By 14mg copper powder (particle diameter=100 order, 2.2 × 10
-4mol), 278mg Br-PtBA-Br (1 × 10
-4mol, 2780g/mol) add in ampoul tube N2 displacement five times.Add 1mL degassed containing 46mg Me
6tREN (2 × 10
-4mol), 17.7 μ L DPE (1 × 10
-4mol) toluene solution.Under room temperature, react termination reaction 6 hours.Polymkeric substance is dissolved in acetone, through aluminum oxide, crosses post copper removal, concentrated, methanol/water precipitation, and 40 ℃ of vacuum-dryings are spent the night.Resulting polymers is tested through gel permeation chromatography (GPC): M
n=7660g/mol, PDI=2.42.
The degraded of embodiment 19 multi-block polymers
The many blocks polystyrene 20mg that gets example 7, is dissolved in 1mL dimethylbenzene, opens wide in system, reacts 6 hours at 130 ℃.Polymkeric substance is tested through gel permeation chromatography (GPC): M
n=1200g/mol, PDI=1.10.
Claims (4)
1. the preparation method of a degradable multiblock polymer, under the condition that it is characterized in that existing at solvent, the polyamines of the polymkeric substance that is halogen by 1 mole of terminal functionality and 0.5～5 mole of free radical scavenger, the metallic copper of 2～10 moles or mantoquita and 2～10 moles adds in reactor, stir, after deoxidation, 10～100 ℃ are reacted 0.1～24 hour, obtain degradable multiblock polymer; Described terminal functionality is that the polymkeric substance of halogen is: α-brominated Polystyrene, α, ω-brominated Polystyrene, α-bromination polyacrylic acid tert-butyl ester, α, ω-bromination polyacrylic acid tert-butyl ester, α, ω-bromination polycaprolactone, α, ω-brominated Polystyrene-b-polyacrylic acid tert-butyl ester, α, ω-bromination polyethylene oxide-b-poly(propylene oxide) or α, ω-brominated Polystyrene-b-polypropylene; Described free radical scavenger is: 2-methyl-2-nitroso-group propane, 1，1-diphenylethylene or 4,4 '-bis-(dimethylamino) sulfo-benzophenone.
2. the preparation method of a kind of degradable multiblock polymer according to claim 1, is characterized in that described metallic copper is copper powder, copper wire or copper sheet.
3. the preparation method of a kind of degradable multiblock polymer according to claim 2, is characterized in that described mantoquita is: Red copper oxide, cuprous sulfide, cuprous telluride, selenkupfer, cuprous bromide, cuprous chloride or cuprous iodide.
4. the preparation method of a kind of degradable multiblock polymer according to claim 1, it is characterized in that described polyamines is 2, 2 '-dipyridyl, 4, 4 '-bis-(5-nonyls)-2, 2 '-dipyridyl, 1, 10-phenanthroline, N, N, N ', N '-Tetramethyl Ethylene Diamine, N-propyl group-(2-pyridyl) methylamine, 2, 2 ': 6 ', 2 "-terpyridyl, 4, 4 ', 4 "-tri-(5-nonyls)-2, 2 ': 6 ', 2 "-terpyridyl, N, N, N ', N ", N "-pentamethyl-diethyl triamine, N, N-bis-(2-pyridylmethyl) octylame, 1, 1, 4, 7, 10, 10-hexamethyl trientine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
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| WO2000018807A1 (en) * | 1998-09-29 | 2000-04-06 | Ciba Specialty Chemicals Holding Inc. | Process for the preparation of polymers containing n→o terminal groups |
| CN1277214A (en) * | 2000-06-23 | 2000-12-20 | 复旦大学 | Superbranched polystyrene and its preparation |
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