CN102746515B - Method for preparing block copolymers - Google Patents
Method for preparing block copolymers Download PDFInfo
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- CN102746515B CN102746515B CN 201210245317 CN201210245317A CN102746515B CN 102746515 B CN102746515 B CN 102746515B CN 201210245317 CN201210245317 CN 201210245317 CN 201210245317 A CN201210245317 A CN 201210245317A CN 102746515 B CN102746515 B CN 102746515B
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- 238000000034 method Methods 0.000 title abstract description 21
- 229920001400 block copolymer Polymers 0.000 title abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 7
- -1 4-(dimethylamino) phenyl Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 abstract description 45
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract description 28
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 64
- 238000005227 gel permeation chromatography Methods 0.000 description 44
- 239000004793 Polystyrene Substances 0.000 description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 32
- 238000012360 testing method Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 15
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- 229920002223 polystyrene Polymers 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 13
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 238000005859 coupling reaction Methods 0.000 description 12
- 239000003999 initiator Substances 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 239000012141 concentrate Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000003708 ampul Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- 0 CCC(C(C)(C)*C(C)C(*)(CC)C(O*)=O)c1ccc(*)cc1 Chemical compound CCC(C(C)(C)*C(C)C(*)(CC)C(O*)=O)c1ccc(*)cc1 0.000 description 4
- 229940123457 Free radical scavenger Drugs 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 229920000314 poly p-methyl styrene Polymers 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000007342 radical addition reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FQFILJKFZCVHNH-UHFFFAOYSA-N tert-butyl n-[3-[(5-bromo-2-chloropyrimidin-4-yl)amino]propyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCCNC1=NC(Cl)=NC=C1Br FQFILJKFZCVHNH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical compound CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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 ketoneserving 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 by the different monomer polymerization of continuous initiation.Simultaneously, utilize combination between the different polymerization processs can synthesize the segmented copolymer of different structure.But this segmented copolymer that obtains by 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 (as molecular weight and molecular weight distribution).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.
2005 (Chemical Communications, 2005,57 – 59) such as Jan C.M.van Hest have reported the novel method that a kind of segmented copolymer is synthetic.They utilize the bromide that contains triple bond functional group as initiator, are the polymkeric substance (as PMMA, PS etc.) of triple bond by the synthetic end group of atomic radical transfer polymerization reaction (ATRP); On the other hand, by the end group polymkeric substance that to modify synthetic end group be azido group (as 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 steps more complicated is unfavorable for carrying out scale operation.
The free radical coupling reaction can be for the synthesis of the polymkeric substance (Progress in Polymer Science, 2012,37,1004 – 1030) of different structure.The direct coupling under the effect of Cu/ part of alpha-brominated polymkeric substance can only obtain the bi-block copolymer of symmetry.(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 by regulating two kinds of alpha-brominated things etc., the highlyest can only reach 56% cross coupling rate, 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 by the method for direct coupling
A-P
B).
Free radical addition-coupled reaction is a kind of reaction efficiently, bromide produces free radical under copper/part effect, addition reaction takes place with free radical scavenger (double bond compound), original position generates stabilized radical, this stabilized radical and another molecule free radical generation coupled reaction subsequently can be for the synthesis of multi-block polymer (Journal ofPolymer Science:Part A:Polymer Chemistry, 2011,49,612-618; 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 by 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 deficiencies in the 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, 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-is
R
1Be hydrogen atom or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl, R
3Be phenyl, cyano group, the tertiary butyl or 4-(dimethylamino) phenyl.
Described alpha-brominated polymer P
AThe molecular structural formula of-Br is:
Wherein, R
1Be hydrogen atom 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 hydrogen atom or methyl.
The molecular structural formula of described double bond compound is:
Wherein, R
1Be hydrogen atom or methyl, R
3Be phenyl, cyano group, 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, the double bond compound convenient sources is (as 1,1-diphenylethlene and thiomicoler's ketone are commercialization reagent), alpha-brominated polymkeric substance can be by 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 height, 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 addition rate constant and the coupling rate constant of free radical scavenger (double bond compound), can obtain segmented copolymer (be example with the 1).The preparation method's of segmented copolymer reaction formula is
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, 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-is
R
1Be hydrogen atom or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl, R
3Be phenyl, cyano group, the tertiary butyl or 4-(dimethylamino) phenyl.
Described alpha-brominated polymer P
AThe molecular structural formula of-Br is:
Wherein, R
1Be hydrogen atom 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 hydrogen atom or methyl.
The molecular structural formula of described double bond compound is:
Wherein, R
1Be hydrogen atom or methyl, R
3Be phenyl, cyano group, 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 illustrates with the following examples, 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) by the synthetic alpha-brominated polystyrene (PS-Br) of atom transfer radical polymerization (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) by the synthetic alpha-brominated polyacrylic acid tert-butyl ester (PtBA-Br) of atom transfer radical polymerization (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 polystyrene PS-Br of 110mg, the alpha-brominated polyacrylic acid 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 tetrahydrofuran (THF) add in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Add the 14mg copper powder under the nitrogen.Reacted 24 hours down at 25 ℃.Product is diluted with tetrahydrofuran (THF), cross the post copper removal through neutral alumina, concentrate, 50 ℃ of vacuum-dryings are spent the night.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, the CH of 20mL drying
2Cl
2Slowly drip the CH that contains the 2mL2-bromopropionyl bromide under the ice bath
2Cl
2Solution 20mL.Dropwise in half an hour.Slowly rise to room temperature, stirring is spent the night.Remove by filter the white particle precipitation.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 anhydrous MgSO in back
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) by the synthetic alpha-brominated polystyrene (PS-Br) of atom transfer radical polymerization (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 polystyrene PS-Br of 280mg, 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 tetrahydrofuran (THF) adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Add the 140mg copper powder under the nitrogen.Reacted 24 hours down at 65 ℃.Product is diluted with tetrahydrofuran (THF), cross the post copper removal through neutral alumina, concentrate, 50 ℃ of vacuum-dryings are spent the night.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) by the synthetic alpha-brominated polymethyl acrylate (PMA-Br) of atom transfer radical polymerization (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) by the synthetic alpha-brominated polystyrene (PS-Br) of atom transfer radical polymerization (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 polystyrene PS-Br of 280mg, 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 tetrahydrofuran (THF) adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Add the 14mg copper powder under the nitrogen.Reacted 24 hours down at 45 ℃.Product is diluted with tetrahydrofuran (THF), cross the post copper removal through neutral alumina, concentrate, 50 ℃ of vacuum-dryings are spent the night.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) by the synthetic alpha-brominated polymethyl acrylate (PMA-Br) of atom transfer radical polymerization (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) by the synthetic alpha-brominated polystyrene (PS-Br) of atom transfer radical polymerization (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 polystyrene PS-Br of 76mg, 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 tetrahydrofuran (THF) adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Add the 14mg copper powder under the nitrogen.Reacted 24 hours down at 45 ℃.Product is diluted with tetrahydrofuran (THF), cross the post copper removal through neutral alumina, concentrate, 50 ℃ of vacuum-dryings are spent the night.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) by the synthetic alpha-brominated polymethyl acrylate (PMA-Br) of atom transfer radical polymerization (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) by the synthetic alpha-brominated polystyrene (PS-Br) of atom transfer radical polymerization (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 polystyrene PS-Br of 460mg, 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 tetrahydrofuran (THF) adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Add the 14mg copper powder under the nitrogen.Reacted 24 hours down at 45 ℃.Product is diluted with tetrahydrofuran (THF), cross the post copper removal through neutral alumina, concentrate, 50 ℃ of vacuum-dryings are spent the night.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) by the synthetic alpha-brominated polymethylmethacrylate (PMMA-Br) of atom transfer radical polymerization (ATRP) method: with 2-isobutyl ethyl bromide (2-EBiB) as initiator, [methyl methacrylate]
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 polystyrene PS-Br(M of 280mg
n=2800g/mol), and the alpha-brominated polymetylmethacrylate-Br of 400mg, 18mg1,1-diphenylethlene (DPE), 50mg2,2 '-dipyridyl, 2mL tetrahydrofuran (THF) add in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Add the 14mg copper powder under the nitrogen.Reacted 24 hours down at 45 ℃.Product is diluted with tetrahydrofuran (THF), cross the post copper removal through neutral alumina, concentrate, 50 ℃ of vacuum-dryings are spent the night.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, the CH of 20mL drying
2Cl
2Slowly drip the CH that contains 2mL2-bromo isobutyl acylbromide under the ice bath
2Cl
2Solution 20mL.Slowly rise to room temperature, stirring is spent the night.Filter, filtrate is used the 1M HCl aqueous solution, 5%NaHCO respectively
3The aqueous solution, deionized water and saturated NaCl solution washing, organic layer merge the anhydrous MgSO in back
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) by the synthetic alpha-brominated poly-p-methylstyrene (PMS-Br) of atom transfer radical polymerization (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 poly-p-methylstyrene PMS-Br 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 tetrahydrofuran (THF) add in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Add the 7.1mg copper powder under the nitrogen.Reacted 24 hours down at 25 ℃.Product is diluted with tetrahydrofuran (THF), cross the post copper removal through neutral alumina, concentrate, 50 ℃ of vacuum-dryings are spent the night.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: embodiment 2(1).
(2) by the synthetic alpha-brominated polystyrene (PS-Br) of atom transfer radical polymerization (ATRP) method: embodiment 5(2).
(3) segmented copolymer PEG-b-PS is synthetic: with the alpha-brominated polystyrene 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, the 2mL tetrahydrofuran (THF) adds in the ampoule, and the freezing-degassing-fusion circulation is removed oxygen three times.Add the 28mg copper powder under the nitrogen.Reacted 24 hours down at 35 ℃.Product is diluted with tetrahydrofuran (THF), cross the post copper removal through neutral alumina, concentrate, 50 ℃ of vacuum-dryings are spent the night.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 (2)
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, 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
BContain link unit-X-, molecular structural formula is:
Or
Wherein ,-X-is
Or
R
1Be hydrogen atom or methyl, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or the tertiary butyl, R
3Be phenyl, cyano group, the tertiary butyl or 4-(dimethylamino) phenyl;
Described alpha-brominated polymer P
AThe molecular structural formula of-Br is:
Wherein, R
1Be hydrogen atom 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 hydrogen atom or methyl;
Described double bond compound molecular structural formula is:
Wherein, R
1Be hydrogen atom or methyl, R
3Be phenyl, cyano group, the tertiary butyl or 4-(dimethylamino) phenyl.
2. 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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