CN102010507B - Method for preparing copolymer with multielement alternating structure - Google Patents
Method for preparing copolymer with multielement alternating structure Download PDFInfo
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- CN102010507B CN102010507B CN2010105089189A CN201010508918A CN102010507B CN 102010507 B CN102010507 B CN 102010507B CN 2010105089189 A CN2010105089189 A CN 2010105089189A CN 201010508918 A CN201010508918 A CN 201010508918A CN 102010507 B CN102010507 B CN 102010507B
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- dibromo
- alternating structure
- polynary
- multipolymer
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- 238000000034 method Methods 0.000 title abstract description 10
- 229920001577 copolymer Polymers 0.000 title abstract 5
- 239000010949 copper Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- -1 dibromo compound Chemical class 0.000 claims abstract description 14
- 150000002832 nitroso derivatives Chemical class 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 229920000768 polyamine Polymers 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical group OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- IOWXPACCEDZPAV-UHFFFAOYSA-N BrC(C)CCCCCCCCCCC(C)Br Chemical compound BrC(C)CCCCCCCCCCC(C)Br IOWXPACCEDZPAV-UHFFFAOYSA-N 0.000 claims description 7
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Natural products CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- OWOUZKDXOCXWJJ-UHFFFAOYSA-N dimethyl 2,7-dibromooctanedioate Chemical compound COC(=O)C(Br)CCCCC(Br)C(=O)OC OWOUZKDXOCXWJJ-UHFFFAOYSA-N 0.000 claims description 3
- ZDJFDFNNEAPGOP-UHFFFAOYSA-N tetradecanedioic acid dimethyl ester Natural products COC(=O)CCCCCCCCCCCCC(=O)OC ZDJFDFNNEAPGOP-UHFFFAOYSA-N 0.000 claims description 3
- 125000006479 2-pyridyl methyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 claims description 2
- MZEWONGNQNXVKA-UHFFFAOYSA-N [Cu].[Cu].[Te] Chemical compound [Cu].[Cu].[Te] MZEWONGNQNXVKA-UHFFFAOYSA-N 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 150000001879 copper Chemical class 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 230000003407 synthetizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000012141 concentrate Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 150000002978 peroxides Chemical class 0.000 description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 4
- 101150065749 Churc1 gene Proteins 0.000 description 4
- 102100038239 Protein Churchill Human genes 0.000 description 4
- 125000006414 CCl Chemical group ClC* 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000668 atmospheric pressure chemical ionisation mass spectrometry Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- DONKHOLEGZZEHX-UHFFFAOYSA-N dimethyl 2,13-dibromotetradecanedioate Chemical compound COC(=O)C(Br)CCCCCCCCCCC(Br)C(=O)OC DONKHOLEGZZEHX-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000950 dibromo group Chemical class Br* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for preparing a copolymer with a multielement alternating structure. The method comprises the following steps of: in the presence of a solvent, adding 1mol of nitroso compound, 0.5 to 5mol of dibromo compound, 1 to 10mol of metallic copper or copper salt and 1 to 10mol of polyamine to a reactor and stirring, and reacting for 0.1 to 24 hours at the temperature of 10 to 100 DEG C after deoxidized to obtain the copolymer with the multielement alternating structure. The invention has simple synthetic method and mild reaction condition and can utilize the dibromo compound with different structures to be reacted with the nitroso compound to obtain the copolymer with the multielement alternating structure. The invention overcomes defects of the traditional methods, synthesizes the high molecular weight (Mn>50,000g/mol) copolymer with the multielement alternating structure, and expands the new method for synthetizing high molecules.
Description
Technical field
The present invention relates to the preparation method of polymkeric substance, relate in particular to a kind of preparation method with multipolymer of polynary alternating structure.
Background technology
Synthetic polymkeric substance with polynary alternating structure is the target and the challenge in Polymer Synthesizing field.Though adopt traditional copolymerization can obtain containing the polymkeric substance of multiple monomeric unit, the sequential structure of comonomer but is difficult to accurately control.Have only some special monomers can obtain the multipolymer of strict binary alternatively structure, like vinylbenzene and maleic anhydride through copolymerization.In recent years, during the article of relevant polymer sequence array structure control report is arranged, but existing means can't accomplish also high molecular secondary structure is realized complete controllable polymerization.However, the possibility (PolymerChemistry, 1,55-62,2010) that still has many example let us to see to realize this goal.
(Nature Communication such as Satoh; 1-6,2010) the C-Cl key through designing a kind of C=C of containing key and having reactive behavior is through the continuous atom transferred free radical addition (ATRA) of metal catalysed reaction; C-Cl key and C=C key are reacted; Form C-C key and active lower C-Cl key, obtain main chain and contain vinylbenzene, (ABC) with ternary alternating structure of propenoate and vinylchlorid
nThe type polymkeric substance.But this reaction has certain limitation, has a certain proportion of side reaction, and the polymericular weight that obtains is also lower.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method with polynary alternating structure multipolymer is provided.
Preparing method with polynary alternating structure multipolymer is under the condition that solvent exists; 1 mole of nitroso compound, 0.5～5 mole of dibromo compound, 1～10 mole metallic copper or mantoquita and 1～10 mole polyamine are added in the reactor drum; Stir; After the deoxidation, 10～100 ℃ were reacted 0.1～24 hour, and obtained having polynary alternating structure multipolymer.
Described molecular structural formula with polynary alternating structure multipolymer is:
Wherein, R
1Be sec.-propyl, tertiary butyl, phenyl, 2,3,4,5,6-pentamethyl-phenyl, 4-hydroxy phenyl, 4-aminophenyl or cyanic acid, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or tertiary butyl, n=1,2,3 or 5.
Described dibromo compound is: 2, and 5-dibromo diethylene adipate, 2,7-dibromo suberic acid dimethyl ester, 2; 7-dibromo suberic acid di tert butyl carbonate, 2; 13-dibromo tetradecanedioic acid dimethyl ester, 2,13-dibromo tetradecane diacid diethyl ester, 2,13-dibromo tetradecane diacid dipropyl, 2; 13-dibromo tetradecane diacid diisopropyl ester, 2,13-dibromo tetradecane diacid di-n-butyl, to (brooethyl) benzene, two (2-bromine isobutyl acyloxy) ethane or two (2-bromine isobutyl acyloxy) hexane.
Described nitroso compound molecular structural formula is:
Wherein, R
1Be sec.-propyl, tertiary butyl, phenyl, 2,3,4,5,6-pentamethyl-phenyl, 4-hydroxy phenyl, 4-aminophenyl or cyanic acid.
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 polyamine is 2,2 '-dipyridyl, 4,4 '-two (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 "-three (5-nonyl)-2,2 ': 6 ', 2 "-terpyridyl, N, N; N ', N ", N "-pentamethyl-diethyl triamine, N, N-two (2-pyridylmethyl) octylame, 1,1; 4,7,10,10-hexamethyl triethyl tetramine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
The present invention synthesizes a series of dibromo compounds; Through generating active diradical,, realize progressively polymerization of free radical addition-coupling with the nitroso compound reaction with metal or metallic salt reaction; It is regular to obtain the sequence monomer distribution, the polynary alternating copolymer that molecular weight is higher.The end group level of response of this method can go for the synthetic of different functional groups polymkeric substance simultaneously near 100%, proposed a kind of polymkeric substance synthetic novel method of synthetic polynary alternating structure, and the monomer scope that is suitable for is wide.The present invention overcomes the deficiency of existing method, synthetic HMW (M with polynary alternating structure
n＞50000g/mol) polymkeric substance has been expanded the novel method of Polymer Synthesizing.
Embodiment
The present invention explains with following embodiment, but scope of the present invention is not limited to these embodiment.
All polymeric reaction conditions are under the reaction conditions of anaerobic, to carry out.
The nitroso compound molecular formula that is used for embodiment is as follows:
The dibromo compound molecular formula that is used for embodiment is as follows:
Embodiment 12,5-dibromo diethylene adipate (DEDBA) and 2-methyl-2-nitroso-group propane (MNP) reaction
With 70.4mg Cu powder (1.1mmol), 180mg DEDBA (0.5mmol), 43.5mg MNP (0.5mmol) adds in the ampoul tube nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Under 25 ℃, reaction 30min, liquid nitrogen quenching termination reaction.Polymkeric substance is dissolved in the acetone, crosses the post copper removal through neutral alumina, concentrates 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=8360g/mol, molecular weight distributing index (PDI)=2.35.
Embodiment 22,7-dibromo suberic acid dimethyl ester (DMDBO) and 2-methyl-2-nitroso-group propane (MNP) reaction
2,7-dibromo suberic acid dimethyl ester (DMDBO) synthetic: with 5.23g (0.03mol) suberic acid, 5.4mL (0.075mol) thionyl chloride adds in the Schlenk bottle of 25mL, is heated to 80 ℃, reacts 1.5 hours.Stop heating, remaining thionyl chloride in the Schlenk bottle is removed.The Schlenk bottle is heated to 85 ℃, with the liquid bromine (Br of 3.9mL (0.076mmol)
2) several times (each 0.5mL) slowly add the Schlenk bottle, added in 6 hours.85 ℃ are continued down to stir 3 hours.The reaction solution of heat is dropwise added in the 50mL ice bath refrigerative absolute methanol solution, rise to room temperature, stirred overnight.Methanol solution poured in 0 ℃ the deionized water, obtain yellow troubled liquor.With 5 * 30mL CH
2Cl
2Extraction merges organic layer.Organic layer is used 3 * 25mL 2%Na respectively
2SO
3The aqueous solution, 2%NaHCO
3The aqueous solution, deionized water wash, anhydrous MgSO
4Dry.Filter, concentration of reaction solution, recrystallizing methanol obtains white crystal 10g, yield 93%.The compound characterization result is following:
1H NMR (400MHz, CDCl
3): 4.21-4.25 (m, CHCH
2), 3.80 (s, 6H, OCH
3), 1.97-2.14 (m, 4H, CHCH
2), 1.35-1.60 (m, 4H, CH
2(CH
2)
2CH
2).
13C?NMR(100MHz，CDCl
3)：26.32(CH
2(CH
2)
2CH
2)，34.35(2CHCH
2)，45.14-45.18(2CHCH
2)，52.83(2OCH
3)，170.00(2C＝O)。Results of elemental analyses, theoretical value: C, 33.36%; H, 4.48%.Measured value: C, 33.25%; H, 4.46%.APCI-MS result: 361.6 [M+1]
+, 201.6 [M-2Br+H]
+
With 70.4mg Cu powder (1.1mmol), 180mg DMDBO (0.5mmol), 43.5mg MNP (0.5mmol) adds in the ampoul tube nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Under 25 ℃, reacted liquid nitrogen quenching termination reaction 30 minutes.Polymkeric substance is dissolved in the acetone, crosses the post copper removal through neutral alumina, concentrates 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=10200g/mol, molecular weight distributing index (PDI)=3.16.
Embodiment 3-8 2,13-dibromo tetradecanedioic acid dimethyl ester (DMDBT) and 2-methyl-2-nitroso-group propane (MNP) reaction
2,13-dibromo tetradecanedioic acid dimethyl ester (DMDBT) synthetic: with 5.16g (0.02mol) tetradecane diacid, 4.3mL (0.06mol) thionyl chloride adds in the Schlenk bottle of 25mL, is heated to 80 ℃, reacts 1.5 hours.Stop heating, remaining thionyl chloride in the Schlenk bottle is removed.The Schlenk bottle is heated to 85 ℃, with the Br of 2.6mL (0.05mmol)
2(each 0.5mL) slowly adds the Schlenk bottle several times, adds in 4 hours.85 ℃ are continued down to stir 3 hours.The reaction solution of heat is dropwise added in the 40mL ice bath refrigerative absolute methanol solution, rise to room temperature, stirred overnight.Methanol solution is poured in the deionized water of 0 ℃ of 80mL, obtained yellow troubled liquor.With 5 * 30mL CH
2Cl
2Extraction merges organic layer.Organic layer is used 3 * 25mL 2%Na respectively
2SO
3The aqueous solution, 2%NaHCO
3The aqueous solution, deionized water wash, anhydrous MgSO
4Dry.Filter, concentration of reaction solution, the crystallization of methylene chloride (v/v=1/2) solution weight obtains light beige solid 5.3g, yield 60%.The compound characterization result is following:
1H NMR (400MHz, CDCl
3): 4.20-4.24 (m, 2H, CHCH
2), 3.78 (s, 6H, OCH
3), 1.93-2.11 (m, 4H, CHCH
2), 1.26-1.52 (m, 16H, CH
2(CH
2)
8CH
2).
13C?NMR(100MHz，CDCl
3)：27.10，28.65，29.11，29.22(CH
2(CH
2)
8CH
2)，34.79(2CHCH
2)，45.64(2CHCH
2)，52.74(2OCH
3)，170.26(2C＝O)。Results of elemental analyses: theoretical value: C, 43.26%; H, 6.35%.Measured value: C, 43.20%; H, 6.36%.APCI-MS：445.7[M+1]
+。
With 70.4mg Cu powder (1.1mmol), 222mg DMDBT (0.5mmol), 43.5mg MNP (0.5mmol) adds in the ampoul tube nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.React different time under the room temperature.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.
The molecular weight of the polymkeric substance of the prepared acquisition of embodiment 3-8 and distribution thereof are shown in table one.
Table one
2 of embodiment 9-15 different mol ratio, 13-dibromo tetradecanedioic acid dimethyl ester (DMDBT) and 2-methyl-2-nitroso-group propane (MNP) reaction
With 70.4mg Cu powder (1.1mmol), the DMDBT (shown in table two) of 43.5mg MNP (0.5mmol) and corresponding mol ratio amount adds in the ampoul tube, nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Termination reaction, reaction is 30 minutes under the room temperature.Polymkeric substance is dissolved in the acetone, crosses the post copper removal through neutral alumina, concentrates 50 ℃ of vacuum-drying 24 hours.
The molecular weight of the polymkeric substance of the prepared acquisition of embodiment 9-12 and distribution thereof are shown in table two.
Table two
Embodiment 162,13-dibromo tetradecane diacid diethyl ester (DEDBT) and 2-methyl-2-nitroso-group propane (MNP) reaction
2,13-dibromo tetradecane diacid diethyl ester (DEDBT) synthetic: with 5.16g (0.02mol) tetradecane diacid, 3.6mL (0.05mol) thionyl chloride (SOCl
2) add in the Schlenk bottle of 25mL, be heated to 80 ℃, begin to reflux, reacted 1.5 hours.Stop heating, with remaining SOCl in the Schlenk bottle
2Remove.Be heated to 85 ℃, with the Br of 2.6mL (0.05mmol)
2Slowly add the Schlenk bottle several times, added in 4 hours.85 ℃ are continued down to stir 3 hours.The reaction solution of heat is dropwise added in the 40mL ice bath refrigerative ethanol solution, rise to room temperature, stirred overnight.Ethanolic soln is poured in the deionized water of 0 ℃ of 80mL, obtained yellow troubled liquor.With 5 * 30mL CH
2Cl
2Extraction merges organic layer.Organic layer is used 3 * 25mL 2%Na respectively
2SO
3The aqueous solution, 2%NaHCO
3The aqueous solution, deionized water wash, anhydrous MgSO
4Dry.Filter, concentration of reaction solution with the crystallization of methylene chloride (v/v=1/5) solution weight, obtains faint yellow solid.The compound characterization result is following:
1H NMR (400MHz, CDCl
3): 4.17-4.26 (m, 6H ,-CHCH
2With-OCH
2CH
3), 1.92-2.10 (m, 4H ,-CHCH
2), 1.26-1.56 (m, 22H ,-CH
2(CH
2)
8CH
2-with-OCH
2CH
3).Results of elemental analyses theoretical value: C, 43.26%; H, 6.35%.Measured value: C, 43.20%; H, 6.36%.APCI-MS：445.7[M+1]
+。
With 70.4mg Cu powder (1.1mmol), 43.5mg MNP (0.5mmol) and 236mg DEDBT (0.5mmol) add in the ampoul tube, nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Reaction is 30 minutes under the room temperature.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=57200g/mol, molecular weight distributing index (PDI)=3.01.
Embodiment 17 2,13-dibromo tetradecanedioic acid dimethyl ester (DMDBT) and nitrosobenzene (NB) reaction
With 320mg Cu powder (5mmol), 54mgNB (0.5mmol) and 222mg DMDBT (0.5mmol) add in the ampoul tube, nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Reaction is 30 minutes under the room temperature.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=19800g/mol, molecular weight distributing index (PDI)=3.22.
Embodiment 18 2 (2-bromine isobutyl acyloxy) ethane (BBiBE) and 2-methyl-2-nitroso-group propane (MNP) reaction
Synthesizing of two (2-bromine isobutyl acyloxy) ethane (BBiBE): with 1.1mL terepthaloyl moietie (0.02mol); 8.7mL triethylamine (0.06mL) is dissolved in the 50mL methylene dichloride; Place the 250mL there-necked flask, the ice bath cooling, slowly Dropwise 5 0mL contains the dichloromethane solution of 7.4mL 2-bromo isobutyl acylbromide (0.06mol); Dripped off stirred overnight under the room temperature in 2 hours.Filter, filtrating is used 5%NaHCO
3Solution washing 3 times, deionized water water washing 3 times, anhydrous magnesium sulfate drying concentrates, and uses recrystallizing methanol, obtains colourless acicular crystal, yield 78%.Test result is following:
1H NMR (400MHz, CDCl
3): 1.93 (CH
3), 3.70 (OCH
2);
13C NMR:56.63 (OCH
2), 75.72 (C-Br), 171.12 (C=O).
With 70.4mg Cu powder (1.1mmol), 43.5mg MNP (0.5mmol) and 180mg BBiBE (0.5mmol) add in the ampoul tube, nitrogen replacement three times.Add the PMDETA 208 μ L (1mmol) that remove peroxide, THF 1mL.Reaction is 30 minutes under the room temperature.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=31200g/mol, molecular weight distributing index (PDI)=2.23.
Embodiment 19 2 (2-bromine isobutyl acyloxy) ethane (BBiBE) and nitrosobenzene (NB) reaction
With 32mg Cu powder (0.5mmol), 54mg NB (0.5mmol), 78mg 2, and 2-dipyridyl (0.5mmol) 180mg BBiBE (0.5mmol) adds in the ampoul tube, nitrogen replacement three times.Add the THF 1mL that removes peroxide.100 ℃ were reacted 2 hours down.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate 50 ℃ of vacuum-drying 24 hours.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=21800g/mol, molecular weight distributing index (PDI)=3.12.
Embodiment 20 is to (brooethyl) benzene and 2-methyl-2-nitroso-group propane (MNP) reaction
With 70.4mg Cu powder (1.1mmol), 43.5mg MNP (0.5mmol), 132mg adds in the ampoul tube nitrogen replacement three times to (brooethyl) benzene (0.5mmol) and 290mg three [(2-pyridyl) methyl] amine (1mmol).Add the toluene 1mL that removes peroxide.10 ℃ were reacted 24 hours down.Termination reaction, polymkeric substance are dissolved in the acetone, cross the post copper removal through neutral alumina, concentrate, and 50 ℃ of vacuum-drying 24 hours obtains white powder.Resulting polymers is tested through gel permeation chromatography (GPC): number-average molecular weight (M
n)=30100g/mol, molecular weight distributing index (PDI)=2.98.
Claims (6)
1. preparation method with polynary alternating structure multipolymer; It is characterized in that under the condition that solvent exists; 1 mole of nitroso compound, 0.5～5 mole of dibromo compound, 1～10 mole metallic copper or mantoquita and 1～10 mole polyamine are added in the reactor drum, stir, after the deoxidation; 10～100 ℃ were reacted 0.1～24 hour, and obtained having polynary alternating structure multipolymer; Described molecular structural formula with polynary alternating structure multipolymer is:
Wherein, R
1Be sec.-propyl, tertiary butyl, phenyl, 2,3,4,5,6-pentamethyl-phenyl, 4-hydroxy phenyl, 4-aminophenyl or cyanic acid, R
2Be methyl, ethyl, propyl group, normal-butyl, sec.-propyl or tertiary butyl, n=1,2,3 or 5.
2. a kind of preparation method according to claim 1 with multipolymer of polynary alternating structure; It is characterized in that described dibromo compound is: 2,5-dibromo diethylene adipate, 2,7-dibromo suberic acid dimethyl ester, 2; 7-dibromo suberic acid di tert butyl carbonate, 2; 13-dibromo tetradecanedioic acid dimethyl ester, 2,13-dibromo tetradecane diacid diethyl ester, 2,13-dibromo tetradecane diacid dipropyl, 2; 13-dibromo tetradecane diacid diisopropyl ester, 2,13-dibromo tetradecane diacid di-n-butyl, to (brooethyl) benzene, two (2-bromine isobutyl acyloxy) ethane or two (2-bromine isobutyl acyloxy) hexane.
3. a kind of preparation method with multipolymer of polynary alternating structure according to claim 1 is characterized in that described nitroso compound molecular structural formula is:
Wherein, R
1Be sec.-propyl, tertiary butyl, phenyl, 2,3,4,5,6-pentamethyl-phenyl, 4-hydroxy phenyl, 4-aminophenyl or cyanic acid.
4. a kind of preparation method with multipolymer of polynary alternating structure according to claim 1 is characterized in that described metallic copper is copper powder, copper wire or copper sheet.
5. a kind of preparation method with multipolymer of polynary alternating structure according to claim 1 is characterized in that described mantoquita is: Red copper oxide, cuprous sulfide, cuprous telluride, selenkupfer, cuprous bromide, cuprous chloride or cuprous iodide.
6. a kind of preparation method with multipolymer of polynary alternating structure according to claim 1 is characterized in that described polyamine is 2,2 '-dipyridyl, 4,4 '-two (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 "-and terpyridyl, 4,4 ', 4 "-three (5-nonyls)-2; 2 ': 6 ', 2 "-and terpyridyl, N, N, N '; N ", N "-pentamethyl-diethyl triamine, N, N-two (2-pyridylmethyl) octylame, 1,1; 4,7,10,10-hexamethyl triethyl tetramine, three [2-(dimethylin) ethyl] amine or three [(2-pyridyl) methyl] amine.
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