CN107312114A - A kind of azide polymer with polynorbornene backbone structure and preparation method thereof - Google Patents
A kind of azide polymer with polynorbornene backbone structure and preparation method thereof Download PDFInfo
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- CN107312114A CN107312114A CN201610273494.XA CN201610273494A CN107312114A CN 107312114 A CN107312114 A CN 107312114A CN 201610273494 A CN201610273494 A CN 201610273494A CN 107312114 A CN107312114 A CN 107312114A
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- Prior art keywords
- bis
- enb
- mesylate
- reaction
- polynorbornene
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- 229920000636 poly(norbornene) polymer Polymers 0.000 title claims abstract description 53
- 229920000642 polymer Polymers 0.000 title claims abstract description 46
- 150000001540 azides Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 230000035484 reaction time Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011984 grubbs catalyst Substances 0.000 claims abstract description 14
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims abstract description 14
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical group [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- GUWHRJQTTVADPB-UHFFFAOYSA-N lithium azide Chemical compound [Li+].[N-]=[N+]=[N-] GUWHRJQTTVADPB-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GMRIOAVKKGNMMV-UHFFFAOYSA-N tetrabutylazanium;azide Chemical compound [N-]=[N+]=[N-].CCCC[N+](CCCC)(CCCC)CCCC GMRIOAVKKGNMMV-UHFFFAOYSA-N 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 1
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 claims 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 37
- 235000014443 Pyrus communis Nutrition 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 31
- 239000007787 solid Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 235000019439 ethyl acetate Nutrition 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 10
- 230000004224 protection Effects 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000003380 propellant Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- -1 azido compound Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- ZQTYQMYDIHMKQB-UHFFFAOYSA-N exo-norborneol Chemical compound C1CC2C(O)CC1C2 ZQTYQMYDIHMKQB-UHFFFAOYSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 description 1
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000001935 cyclohexenes Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical class CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/02—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F132/04—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention provides a kind of azide polymer with polynorbornene backbone structure and preparation method thereof.Methods described includes：Step 1, carry out Diels Alder reactions, purification process by reaction raw materials of cis-butenediol and cyclopentadiene after obtain ENB dimethanol；Step 2, by the dissolving of the ENB dimethanol of gained in organic solvent, add methylsufonyl chloride and alkali, the reaction time is to obtain ENB bis-mesylate after 1h~7h, purification process；Step 3, by the dissolving of the ENB bis-mesylate of gained in organic solvent, add Grubbs catalyst and carry out ring opening metathesis polymerisation, reaction time 4h~72h adds terminator terminating reaction, and filtration drying obtains polynorbornene bis-mesylate；Step 4, the polynorbornene bis-mesylate of gained is dissolved in the third organic solvent, adds nitrine reagent, 0~200 DEG C of reaction temperature, 4~64h of reaction time adds water terminating reaction, and filtering is dried under vacuum to constant weight, obtains the azide polymer.
Description
Technical field
Present invention design chemistry and field of new materials, more particularly to a kind of nitrine with polynorbornene backbone structure gather
Compound, and a kind of preparation method of the azide polymer with polynorbornene backbone structure.
Background technology
As the Modern weapon systems such as rocket and guided missile are constantly pursued precision strike and efficient Kill capability, people are to making
Higher and higher requirement is proposed for the energetic material [J.Hazard.Mater.2008,151,289.] of weapon energy carrier.Its
In, the polymer containing energy [National Defense Industry Press of the polymer containing energy, 2011 used as binder；Energetic
Polymers:Binders and Plasticizers for Enhancing Performance.Wiley-VCH Verlag
GmbH, 2012] be energetic material matrix and skeleton, the member such as carbon, the hydrogen for being responsible for being supplied to needed for propellant powder and propellant combustion
Element, and adjust energy characteristics, mechanical property, combustibility and processing characteristics of energetic material etc..In fact, to the polymer containing energy
Use be considered as the key for promoting the development of whole energetic material, be also other military powers skill highly confidential to China
Art.
In polymer containing azido group, the generation heat of azido group is 355kJ/mol, is applied to explosive and propulsion
In agent, the energy of propellant powder and propellant can not only be improved, the ablation to itself weapon and reduction feature can also be reduced
Signal etc..Therefore, with glycidyl azide polymer (GAP), poly- 3- azido-methyls -3- methyl oxygen fourth rings (PAMMO), poly- 3,3- bis-
Azido-methyl oxygen fourth ring (PBAMO) etc. causes various countries' scientific research for the azide polymer with polynorbornene backbone structure of representative
The great attention of personnel.
At present two problems are primarily present in synthesis azide polymer：(1) structure of azide polymer is single, is folded
Nitrogen polyethers, and the usual step of synthesis of monomer is long；(2) synthetic method is two-step method, is first prepared using cation ring-opening polymerization
Azide polymer performed polymer, then itself and isocyanates are subjected to polyaddition reaction.For cation ring-opening polymerization, reaction
Condition is harsher, the more difficult control of polymer relative molecular weight and its distribution, and combined coefficient is not high；And isocyanates participation is anti-
Should be generally very sensitive to moisture.
Therefore, in the urgent need to the novel monomer of development structure and the more synthetic method of practicality and high efficiency, to meet military affairs
Demand of the industry to new azide polymer.
The content of the invention
The present invention solves above-mentioned technical problem, poly- the invention provides a kind of nitrine with polynorbornene backbone structure
Compound, and a kind of preparation method of the azide polymer with polynorbornene backbone structure.
The invention discloses a kind of preparation method of the azide polymer with polynorbornene backbone structure, methods described
Including：
Step 1, carry out after Diels-Alder reactions, purification process by reaction raw materials of cis-butenediol and cyclopentadiene
Obtain the ENB dimethanol with following structural formula (I)；
Step 2, the ENB dimethanol of gained is dissolved in the first organic solvent, add methylsufonyl chloride and
Alkali, the reaction time is 1h~7h, obtains the ENB bis-mesylate with following structural formula (II) after purification process；
Step 3, the ENB bis-mesylate of gained is dissolved in second of organic solvent, adds Grubbs catalysis
Agent carries out ring opening metathesis polymerisation, and the reaction time is 4h~72h, adds terminator terminating reaction, filtration drying is had
The polynorbornene bis-mesylate of following structural formula (III)；
Step 4, the polynorbornene bis-mesylate of gained is dissolved in the third organic solvent, adds nitrine examination
Agent, reaction temperature is 0~200 DEG C, and the reaction time is 4~64h, adds water terminating reaction, and filtering is dried under vacuum to constant weight, obtained
To the azide polymer with polynorbornene backbone structure with following structural formula (IV)；
Alternatively, in the step 1, the mol ratio of the cis-butenediol and the cyclopentadiene is (1:1)~(1:
5)；
Diels-Alder reaction is carried out under vacuo, and reaction temperature is 10~200 DEG C, the reaction time be 8h~
64h。
Alternatively, the purification process in the step 1 and the step 2 is included in filtering, chromatographic column and recrystallization at least
It is a kind of.
Alternatively, in the step 2, the mol ratio of the ENB dimethanol and the methylsufonyl chloride is (1:
2)~(1:4)；
The mol ratio of the methylsufonyl chloride and the alkali is 1:1；
Alkali used is triethylamine, pyridine, sodium hydroxide or sodium carbonate.
Alternatively, in the step 3, the mol ratio of the ENB bis-mesylate and the Grubbs catalyst
For (1000:1)~(1:1)；
The Grubbs catalyst be Grubbs generation catalyst, Grubbs bis- generations catalyst, Grubbs three generations catalyst,
Hoveyda-Grubbs generation catalyst or Hoveyda-Grubbs bis- generations catalyst.
Alternatively, in the step 3, the terminator of addition is vinyl ethyl ether, the Grubbs catalyst with it is described
The mol ratio of terminator is 1:100.
Alternatively, in the step 2 and the step 3, the first described organic solvent or it is described second it is organic molten
Agent is dichloromethane, chloroform, acetone, methanol, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide (DMSO) and N, N- bis-
Any one in methylacetamide.
Alternatively, in the step 4, the chain link mole of the nitrine reagent and the polynorbornene bis-mesylate
Than for (1:1)~(20:1)；
The nitrine reagent is sodium azide, Lithium Azide or tetrabutyl ammonium azide；
The third described solvent is N,N-dimethylformamide or dimethyl sulfoxide (DMSO).
Wherein chain link is a polymerized unit in azide polymer.
According to another aspect of the present invention, a kind of nitrine polymerization with polynorbornene backbone structure is additionally provided
Thing, the azide polymer with polynorbornene backbone structure has said structure formula (IV).
Compared with prior art, the present invention includes advantages below：
(1) azido group is combined with norbornene polymer with the first trial in the present invention, designed new
The azide polymer with polynorbornene backbone structure (structural formula is IV).
(2) ENB glycol (structural formula is II) is prepared with Diels-Alder reactions, reaction equation is seen below, had
Have the advantages that simple to operate, source chemicals be easy to get, product it is easily separated purifying, yield it is high, it is easy safety amplification.
Prior art has prepare compound I, and method is mainly to be prepared by the reduction to corresponding acid anhydrides, but this method is former
Need largely to use reducing agent LiAlH in material4.And there are many deficiencies in the use of the reducing agent：①LiAlH4Use by increase make
The danger of standby technique, is unfavorable for a large amount of preparations of the glycol；②LiAlH4Use will produce the accessory substance such as lithium metaaluminate, after
Extract and separate is difficult in processing, so as to increase the time cost of technique.
(3) ROMP reactions are carried out for the bis-mesylate shown in III to structural formula in the present invention, so that at ambient temperature
The polymer of high functionalization is obtained, is that further functional modification and modification lay the foundation.Compared to traditional radical polymerization
And cationic ring-opening polymerization, have many advantages, such as, such as preparation condition is gentle, and the reaction time is shorter, and resulting materials structure
Accurately, molecular weight distribution is narrower etc..
Brief description of the drawings
Fig. 1 shows a kind of system of azide polymer with polynorbornene backbone structure of one embodiment of the invention
The flow chart of Preparation Method；
Fig. 2 shows the infrared spectrum of the ENB dimethanol of the embodiment of the present invention 1；
Fig. 3 shows the hydrogen nuclear magnetic resonance spectrogram of the ENB dimethanol of the embodiment of the present invention 1；
Fig. 4 shows the carbon-13 nmr spectra figure of the ENB dimethanol of the embodiment of the present invention 1；
Fig. 5 shows the infrared spectrum of the ENB bis-mesylate of the embodiment of the present invention 1；
Fig. 6 shows the hydrogen nuclear magnetic resonance spectrogram of the ENB bis-mesylate of the embodiment of the present invention 1；
Fig. 7 shows the carbon-13 nmr spectra figure of the ENB bis-mesylate of the embodiment of the present invention 1；
Fig. 8 shows the nucleus magnetic hydrogen spectrum figure of the bis-mesylate polymer of the embodiment of the present invention 1；
Fig. 9 shows the infrared spectrum of the polynorbornene diazide of the embodiment of the present invention 1；
Figure 10 shows the solid carbon spectrogram of the polynorbornene diazide of the embodiment of the present invention 1.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, it is below in conjunction with the accompanying drawings and specific real
Applying mode, the present invention is further detailed explanation.
Below by embodiment to the azide polymer of the present invention with polynorbornene backbone structure and its preparation
The implementation process of method is described in detail.
The embodiments of the invention provide a kind of preparation method of the azide polymer with polynorbornene backbone structure, ginseng
Fig. 1 is examined, it illustrates a kind of preparation of azide polymer with polynorbornene backbone structure of one embodiment of the invention
The flow chart of method, the described method comprises the following steps：
Step 101, Diels-Alder reactions, purification process are carried out by reaction raw materials of cis-butenediol and cyclopentadiene
The ENB dimethanol with following structural formula (I) is obtained afterwards.
Diels-Alder reacts also known as Diels-Alder reaction, is a kind of cycloaddition reaction.Conjugated diene and substitution
Alkene (commonly referred to as dienophile) reaction generation substituted cyclohexene.
In this step, as dienophile and cyclopentadiene cycloaddition reaction occurs for cis-butenediol, generates ENB
Dimethanol, ENB dimethanol can be largely prepared by this method.Reaction mechanism is：The highest of divinyl macromer contains electron orbit
Interacted with the lowest unoccupied molecular orbital of dienophile, generate chemical bond.
The mol ratio of cis-butenediol and cyclopentadiene can be (1:1)~(1:5)；
Diels-Alder reactions can be carried out under vacuo, and reaction temperature can be 10~200 DEG C, and the reaction time can be with
For 8h~64h.
The application prepares ENB glycol using Diels-Alder reactions, be easy to get with simple to operate, source chemicals,
The advantages of easily separated purifying of product, high yield, easy safety amplification.
Step 102, gained ENB dimethanol is dissolved in the first organic solvent, add methylsufonyl chloride and
Alkali, the reaction time is 1h~7h, obtains the ENB bis-mesylate with following structural formula (II) after purification process.
In this step, the hydroxyl in ENB dimethanol is as nucleopilic reagent, and attack electrophilic reagent methylsufonyl chloride takes off
Go molecule a HCl, HCl by the amine absorption as acid binding agent, obtain methanesulfonates.
The first used organic solvent can be dichloromethane, chloroform, acetone, tetrahydrofuran, N, N- diformazans
Any one in base formamide, dimethyl sulfoxide (DMSO) and DMAC N,N' dimethyl acetamide.
Used alkali can be organic base, such as triethylamine, pyridine；Can also be inorganic base, such as sodium hydroxide, carbonic acid
Sodium.
The mol ratio of ENB dimethanol and methylsufonyl chloride can be (1:2)~(1:4).
The mol ratio of methylsufonyl chloride and alkali can be 1:1.
Purification process in the step 1 and the step 2 includes at least one of filtering, chromatographic column and recrystallization.
When carrying out recrystallization operation to material, gained material can be carried out by rotating operation separation different material
Recrystallization operation, then by being filtrated to get required material.
Step 103, the ENB bis-mesylate of gained is dissolved in second of organic solvent, adds Grubbs and urge
Agent carries out ring opening metathesis polymerisation, and the reaction time is 4h~72h, adds terminator terminating reaction, filtration drying is had
There is the polynorbornene bis-mesylate of following structural formula (III).
In this step, Grubbs catalyst and ENB bis-mesylate there occurs ring opening metathesis polymerisation.
Ring opening metathesis polymerization (Ring-opening metathesis polymerization, be abbreviated as ROMP) is reacted
Open loop, dystopy and the polymerisation of cycloolefin occur in the presence of catalyst for the cycloolefin with ring strain.ROMP reaction tools
There is following obvious characteristic：1. chain triggers fast, and chain increases slow, almost without chain transfer reaction and chain termination reaction, molecular weight with
Time is linear, is a kind of living polymerization.2. molecular weight is can control, and prepares molecular weight from thousands of to millions of
Polymer.3. the 26S Proteasome Structure and Function of polymer can be adjusted by copolyreaction.4. reaction condition is gentle.5. end can be selected
Only agent come control end-blocking functional group.The These characteristics reacted based on ROMP, this step has that molecular weight of product is controllable, product knot
Structure and function can reconcile reaction condition it is gentle the features such as.
The Grubbs catalyst that the present embodiment is applicable include Grubbs generation catalyst, bis- generations of Grubbs catalyst,
Grubbs three generations catalyst, Hoveyda-Grubbs generation catalyst and Hoveyda-Grubbs bis- generations catalyst, the following is institute
State the structural formula of five Grubbs catalyst：
The mol ratio of ENB bis-mesylate and Grubbs catalyst can be (1000:1)~(1:1).
The terminator of addition can be vinyl ethyl ether, and the mol ratio of Grubbs catalyst and terminator can be 1:100.
Used second of organic solvent can be dichloromethane, chloroform, acetone, tetrahydrofuran, N, N- diformazans
Any one in base formamide, dimethyl sulfoxide (DMSO) and DMAC N,N' dimethyl acetamide.
Step 104, the polynorbornene bis-mesylate of gained is dissolved in the third organic solvent, adds nitrine examination
Agent, reaction temperature is 0~200 DEG C, and the reaction time is 4~64h, adds water terminating reaction, and filtering is dried under vacuum to constant weight, obtained
To the azide polymer with polynorbornene backbone structure with following structural formula (IV).
In this step ,-the OMs in bis-mesylate polymer is preferable leaving group, can be by nucleopilic reagent as folded
Azido group attack in nitrogen reagent, occurs nucleophilic substitution.
The consumption of water can be identical with the consumption of the third used organic solvent.
The process of the azide polymer with polynorbornene backbone structure is described in the present embodiment preparation：
The chain link mol ratio of nitrine reagent and polynorbornene bis-mesylate can be (1:1)~(20:1).
Nitrine reagent can be sodium azide, Lithium Azide or tetrabutyl ammonium azide.
The third solvent can be N,N-dimethylformamide or dimethyl sulfoxide (DMSO).
According to the preparation method of the azido compound described in the present embodiment, the present invention obtains a kind of new having above-mentioned knot
The azido compound of structure formula (I).
ENB skeleton structure in the azide polymer with polynorbornene backbone structure have inner mold and
Two kinds of structures of external form.
To make those skilled in the art more fully understand the present invention, below by way of specific embodiment prepared by the explanation present invention
Azide polymer with polynorbornene backbone structure is the method for polynorbornene diazide.
Embodiment 1
Step (1), the preparation of ENB dimethanol.
Reaction equation is as follows：
Freshly prepd cyclopentadiene (10mL, 0.12mol) and cis-butenediol (5mL, 0.06mol) is taken to be put into stirring
In the 50mL of son reaction bulb, vacuumize, the oil bath put it into after stirring at 200 DEG C continues stirring reaction, about reacts
8h, TLC detection show that cis-butenediol reaction is complete, terminate reaction, add ethyl acetate washing, and revolving removes organic solvent,
8.5g white solid matters are filtrated to get, yield is 96.8%.
Reference picture 2, shows the infrared spectrum of the ENB dimethanol in the embodiment of the present invention 1.Reference picture 3, shows
The hydrogen nuclear magnetic resonance spectrogram of ENB dimethanol in the embodiment of the present invention 1.Reference picture 4, shows the embodiment of the present invention 1
In ENB dimethanol carbon-13 nmr spectra figure.Test data is as follows：
Rf (3)=0.59 [V (EtOAc)/V (PE)=1/1]
1H-NMR(CDCl3,400M)δ(ppm):6.00 (s, 2H), 4.49 (s, 2H), 3.58 (d, J=10.0Hz, 2H),
3.32 (t, J=9.2HZ, 2H), 2.76 (s, 2H), 2.49 (d, J=6.0Hz, 2H), 1.34-1.40 (m, 2H).
13C-NMR(CDCl3,400MHz)δ(ppm):134.8,63.3,49.9,46.5,45.1。
Infrared spectrum IR (KBr, cm-1):3260(s),2962(m),2909(m),2863(s),1465(w),1379(w),
1024(s),985(m),725(w),684(w)。
Analyze above-mentioned test result and understand that this step generates the ENB dimethanol with said structure formula (I).
As shown in Figure 2,3260cm-1Locate as the association peak of hydroxyl formation hydrogen bond, 1024cm-1Locate to shake for O-H in-plane bendings
It is dynamic, 2960cm-1And 2909cm-1It is the stretching vibration of saturated alkane carbon, 1465cm-1And 1437cm-1It is that the bending of methylene is shaken
It is dynamic, further illustrate this step and generate ENB dimethanol.
Step (2), the synthesis of ENB bis-mesylate.
Reaction equation is as follows：
Take ENB glycol (2g, 13mmol) to be put into the single port pear shape bottle equipped with magnetic stir bar 250mL, add two
After chloromethanes (DCM) (20mL), single port pear shape bottle is placed on magnetic stirring apparatus, stirring and dissolving.Until completely dissolved, in frozen water
The MsCl (52mmol, 4.0mL) dissolved in DCM (10mL) is added under the conditions of bath into single port pear shape bottle.Take Et3N
(52mmol, 7.2mL) is dissolved in DCM (20mL), is instilled dropwise in single port pear shape bottle under ice-water bath and nitrogen protection.Room temperature
Under, stirring reaction 1h after the completion of question response, 5mL water quenchings is added into single port pear shape bottle and are gone out reaction.Reaction solution is transferred to a point liquid
In funnel, extracted with 2 × 50mL ethyl acetate, collect upper organic layer, saturated aqueous common salt is rinsed, and adds anhydrous sodium sulfate
It is dried overnight.Finally by reacting liquid filtering, concentrated on a rotary evaporator, ethyl acetate and petroleum ether recrystallization, filtering
Flaxen white powdery solids are obtained, the quality of products therefrom ENB bis-mesylate is 3.78g, and yield is
93.8%.
Reference picture 5, shows the infrared spectrum of the ENB bis-mesylate in the embodiment of the present invention 1.Reference picture 6,
Show the hydrogen nuclear magnetic resonance spectrogram of the ENB bis-mesylate in the embodiment of the present invention 1.Reference picture 7, shows this hair
The carbon-13 nmr spectra figure of ENB bis-mesylate in bright embodiment 1.Test result is as follows：
Rf (3)=0.59 [V (EtOAc)/V (PE)=1/1]；
1H-NMR(400MHz,CDCl3)δ(ppm):6.22(s,2H),4.00-4.04(m,2H),3.89-3.93(m,2H),
3.00 (s, 6H), 2.60 (t, J=3.2Hz, 2H), 1.50 (d, J=1.6Hz, 2H), 1.38 (d, J=8.4Hz, 2H)；
13C-NMR(CDCl3,400MHz)δ(ppm):135.6,69.7,49.2,45.6,41.4.
Infrared spectrum IR (KBr, cm-1):3028(m),2982(s),2940(w),1942(s),1417(w),1342(m),
1215(w),1175(m),952(w),881(w),848(w),744(w),531(w),490(w)。
Analyze above-mentioned test result and understand that this step generates the methanesulfonic acid of ENB two with said structure formula (II)
Ester.
As shown in Figure 5,1175cm-1、952cm-1And 531cm-1Place is the characteristic peak of methanesulfonic acid base, 2982cm-1With
2940cm-1It is the stretching vibration of methylene etc., 1492cm-1And 1342cm-1It is the flexural vibrations of methylene etc., further illustrates
ENB bis-mesylate is generated in this step.
Step (3), the synthesis of polynorbornene bis-mesylate.
Reaction equation is as follows：
Grubbs bis- generations catalyst (0.016mmol, 13.58mg) is taken to be put into equipped with magnetic stir bar 50mL single port pear shape bottles
In.In N2Under protection, 2mL dichloromethane is added into single port pear shape bottle.At room temperature, single port pear shape bottle is placed in magnetic stirring apparatus
On, stir 15 minutes.Then ENB bis-mesylate (3.2mmol, 1g) is taken to be put into equipped with magnetic stir bar 50mL single port
In pear shape bottle.In N2Under protection, dichloromethane (14mL) is added into single port pear shape bottle.At room temperature, single port pear shape bottle is placed in
On magnetic stirring apparatus, stirring and dissolving.Grubbs bis- generations catalyst solutions are slowly injected into bis-mesylate molten with syringe afterwards
In liquid.Stir at room temperature.React after about 4h, point TLC plates judge that reactant reaction completely, adds terminator vinyl ethyl ether
(1.6mmol), separates out product, obtains 0.961g polynorbornene bis-mesylate polymer, yield is 96.1%.
Reference picture 8, shows the nucleus magnetic hydrogen spectrum figure of the bis-mesylate polymer in the embodiment of the present invention 1.Test data
It is as follows：
1H-NMR(CDCl3,400MHz)δ(ppm):5.49 (s, 2H), 4.16 (t, J=9.8Hz, 2H), 3.17 (s, 2H),
2.80(s,2H),1.99(s,2H),1.42(s,2H)。
Analyze above-mentioned test data to understand, the product of this step synthesis is bis-mesylate polymer.
Step (4), the synthesis of polynorbornene diazide.
Reaction equation is as follows：
Polynorbornene bis-mesylate (0.96g, chain link molal quantity 3.1mmol) is taken to be dissolved in DMF
(DMF) (10mL) obtains mixture 1, takes NaN3(0.5g, 7.7mmol), which is dissolved in a certain amount of DMF, obtains mixture 2, will be mixed
Compound 1 is added in mixture 2, after stirring several minutes, reaction solution is transferred in 80 DEG C of oil bath and carries out heating response, is reacted
24h, reaction terminates.After the completion of reaction, excessive water is added in reaction solution, stirred 15 minutes, 1h is stood, 10ml is added
The solid on filter paper is collected in water, filtering, is then rotated again under the conditions of 40 DEG C of oil pump, untill solid constant weight.Weigh, obtain
0.60g polynorbornene diazide solids, yield is 99%.
Fig. 9 shows the infrared spectrum of the polynorbornene diazide in the embodiment of the present invention 1, in figure
2099cm-1The absworption peak at place is the characteristic absorption peak of azido group, illustrates that azido group has been successfully introduced into product.
Figure 10 shows the solid carbon spectrogram of the polynorbornene diazide in the embodiment of the present invention 1, and 140ppm is left
Right peak be main chain be at norborneol olefinic carbon peak, 130ppm at peak away from norborneol olefinic carbon on main chain, 60ppm be even folded
The peak of the carbon of nitrogen groups, 45ppm or so is the peak for not connecting substituent carbon on ENB skeleton, and 39ppm's or so is norborneol
Carbon on alkene end of the bridge, 30ppm or so place is the peak that substituent carbon is connected with ENB.
Embodiment 2
Freshly prepd cyclopentadiene (10mL, 0.12mol) and cis-butenediol (10.7mL, 0.12mol) are taken in stirring
In the reaction bulb for the 50mL for mixing son, vacuumize, the oil bath put it into after stirring at 10 DEG C continues stirring reaction, and reaction is about
64h.TLC detection cis-butenediol reactions are complete, terminate reaction, add ethyl acetate washing, and revolving removes organic solvent, filtering
White solid matter ENB dimethanol is obtained, quality is 17.6g, yield 95.3%.
Take ENB glycol (2g, 13mmol) to be put into the single port pear shape bottle equipped with magnetic stir bar 250mL, add
After DCM (20mL), single port pear shape bottle is placed on magnetic stirring apparatus, stirring and dissolving.Until completely dissolved, under the conditions of ice-water bath
The MsCl (52mmol, 4.0mL) dissolved in tetrahydrofuran (20mL) is added into single port pear shape bottle.Take pyridine (52mmol,
4.2mL) it is dissolved in tetrahydrofuran (30mL), is instilled dropwise in single port pear shape bottle under ice-water bath and nitrogen protection.At room temperature,
Stirring reaction 7h, after after product disappearance, into single port pear shape bottle adding 4mL water quenchings goes out reaction.Then reaction solution is transferred to point
In liquid funnel, extracted with 2 × 50mL ethyl acetate, collect upper organic layer, saturated aqueous common salt is rinsed, and adds anhydrous slufuric acid
Sodium is dried overnight.Finally, by reacting liquid filtering, concentrated on a rotary evaporator, ethyl acetate and petroleum ether recrystallization, mistake
Filter obtains flaxen white powdery solids, and the quality of products therefrom ENB bis-mesylate is 3.81g, and yield is
94.5%.
Grubbs three generations catalyst (0.32mmol, 260mg) is taken to be put into equipped with magnetic stir bar 50mL single port pear shape bottles,
In N2Under protections, 3mL chloroforms are added into single port pear shape bottle, at room temperature, single port pear shape bottle is placed on magnetic stirring apparatus,
Stirring 15 minutes.ENB bis-mesylate (3.2mmol, 1g) is taken to be put into equipped with magnetic stir bar 50mL single port pear shape bottles
In.In N2Under protection, chloroform (17mL) is added into single port pear shape bottle.At room temperature, single port pear shape bottle is placed in into magnetic force to stir
Mix on device, stirring and dissolving.Grubbs three generations's catalyst solutions are slowly injected into ENB bis-mesylate with syringe afterwards
In solution.Stir at room temperature, after reaction about 72h, point TLC plates add terminator vinyl ethyl ether (3.2mmol), analyse product
Go out, obtain 0.952g polynorbornene bis-mesylates, yield is 95.2%.
Take polynorbornene bis-mesylate (0.96g, chain link molal quantity 3.1mmol) to be dissolved in DMF (10mL) to be mixed
Thing 1, takes LiN3(0.30g, 6.2mmol), which is dissolved in a certain amount of DMF, obtains mixture 2, and mixture 1 is added into mixture 2
In, after stirring several minutes, reaction solution, which is transferred in 0 DEG C of ice-water bath, to react, and reaction 64h terminates.After the completion of reaction, by excess
Water is added in reaction solution, is stirred 15 minutes, stands 1h, adds 10ml water, and the solid on filter paper, Ran Hou are collected in filtering
Vacuum drying oven is dried at 40 DEG C, untill solid constant weight.Weigh, obtain 0.60g polynorbornene diazides, yield is
99%.
Embodiment 3
Freshly prepd cyclopentadiene (10mL, 0.12mol) and cis-butenediol (10mL, 0.12mol) are taken in stirring
In the 50mL of son reaction bulb, vacuumize, the oil bath put it into after stirring at 10 DEG C continues stirring reaction, and reaction is about
64h.TLC detection maleic reactions are complete, terminate reaction, add ethyl acetate washing, and revolving removes organic solvent, filtered
To white solid matter ENB dimethanol, quality is 17.6g, and yield is 95.3%.
Take ENB glycol (2g, 13mmol) to be put into the single port pear shape bottle equipped with magnetic stir bar 250mL, add
After DCM (20mL), single port pear shape bottle is placed on magnetic stirring apparatus, stirring and dissolving.Until completely dissolved, under the conditions of ice-water bath
The MsCl (26mmol, 2.0mL) dissolved in DCM (20mL) is added into single port pear shape bottle.Then, take sodium carbonate (26mmol,
2.8g) it is dissolved in DCM (20mL), is instilled dropwise in single port pear shape bottle under ice-water bath and nitrogen protection.At room temperature, stir anti-
About 6h is answered, after after product disappearance, into single port pear shape bottle adding 4mL water quenchings goes out reaction.Then reaction solution is transferred to a point liquid
In funnel, extracted with 2 × 50mL ethyl acetate, collect upper organic layer, saturated aqueous common salt is rinsed, and adds anhydrous sodium sulfate
It is dried overnight.Finally, by reacting liquid filtering, concentrated on a rotary evaporator, ethyl acetate and petroleum ether recrystallization, filtering
Flaxen white powdery solids are obtained, the quality of products therefrom ENB bis-mesylate is 3.81g, and yield is
94.5%.
Grubbs generation catalyst (0.0032mmol, 2.63mg) is taken to be put into equipped with magnetic stir bar 50mL single port pear shape bottles
In, in N2Under protection, 3mL acetone is added into single port pear shape bottle, at room temperature, single port pear shape bottle is placed on magnetic stirring apparatus,
Stirring 15 minutes.ENB bis-mesylate (3.2mmol, 1g) is taken to be put into the 50mL single port pear shape bottles equipped with magnetic stir bar
In.In N2Under protection, acetone (17mL) is added into single port pear shape bottle.At room temperature, single port pear shape bottle is placed in magnetic stirring apparatus
On, stirring and dissolving.Grubbs generation catalyst solutions are slowly injected into bis-mesylate solution with syringe afterwards.Room temperature
Lower stirring.React after 12h, point TLC plates, adding terminator vinyl ethyl ether (0.032mmol) separates out product, obtains 0.942g
Polynorbornene bis-mesylate, yield is 94.2%.
Polynorbornene bis-mesylate (0.96g, chain link molal quantity 3.1mmol) is taken to be dissolved in dimethyl sulfoxide (DMSO) (DMSO)
(10mL) obtains mixture 1, takes tetrabutyl amine azide (17.6g, 62mmol) to be dissolved in a certain amount of DMSO and obtains mixture
2, mixture 1 is added in mixture 2, after stirring several minutes, reaction solution is transferred to heating response in 200 DEG C of oil bath,
React and terminate reaction after 4h.After the completion of reaction, excessive water is added in reaction solution, stirred 15 minutes, 1h is stood, added
The solid on filter paper is collected in 10ml water, filtering, is then rotated again under the conditions of 40 DEG C of oil pump, untill solid constant weight.Claim
Amount, obtains 0.58g polynorbornene diazides, yield is 95%.
Above to a kind of azide polymer with polynorbornene backbone structure provided by the present invention, and a kind of tool
The preparation method for having the azide polymer of polynorbornene backbone structure is described in detail, specific case used herein
Principle and embodiment to the present invention are set forth, and the explanation of above example is only intended to the side for helping to understand the present invention
Method and its core concept；Simultaneously for those of ordinary skill in the art, according to the thought of the present invention, in embodiment
And will change in application, in summary, this specification content should not be construed as limiting the invention.
Claims (9)
1. a kind of preparation method of the azide polymer with polynorbornene backbone structure, it is characterised in that methods described bag
Include：
Step 1, carry out Diels-Alder reactions, purification process by reaction raw materials of cis-butenediol and cyclopentadiene after obtain
ENB dimethanol with following structural formula (I)；
Step 2, the ENB dimethanol of gained is dissolved in the first organic solvent, adds methylsufonyl chloride and alkali, instead
It is 1h~7h between seasonable, the ENB bis-mesylate with following structural formula (II) is obtained after purification process；
Step 3, the ENB bis-mesylate of gained is dissolved in second of organic solvent, adds Grubbs catalyst and enter
Row ring opening metathesis polymerisation, the reaction time is 4h~72h, adds terminator terminating reaction, and filtration drying is obtained with following
The polynorbornene bis-mesylate of structure formula (III)；
Step 4, the polynorbornene bis-mesylate of gained is dissolved in the third organic solvent, adds nitrine reagent, instead
It is 0~200 DEG C to answer temperature, and the reaction time is 4~64h, adds water terminating reaction, and filtering is dried under vacuum to constant weight, had
The azide polymer with polynorbornene backbone structure of following structural formula (IV)；
2. according to the method described in claim 1, it is characterised in that in the step 1, the cis-butenediol and the ring
The mol ratio of pentadiene is (1:1)~(1:5)；
The Diels-Alder reactions are carried out under vacuo, and reaction temperature is 10~200 DEG C, and the reaction time is 8h~64h.
3. according to the method described in claim 1, it is characterised in that：
In the step 1 and the step 2, the purification process includes at least one of filtering, chromatographic column and recrystallization.
4. according to the method described in claim 1, it is characterised in that in the step 2, the ENB dimethanol and institute
The mol ratio for stating methylsufonyl chloride is (1:2)~(1:4)；
The mol ratio of the methylsufonyl chloride and the alkali is 1:1；
Alkali used is triethylamine, pyridine, sodium hydroxide or sodium carbonate.
5. according to the method described in claim 1, it is characterised in that in the step 3, the ENB bis-mesylate
Mol ratio with the Grubbs catalyst is (1000:1)~(1:1)；
The Grubbs catalyst be Grubbs generation catalyst, Grubbs bis- generations catalyst, Grubbs three generations catalyst,
Hoveyda-Grubbs generation catalyst or Hoveyda-Grubbs bis- generations catalyst.
6. according to the method described in claim 1, it is characterised in that in the step 3, the terminator of addition is vinyl second
The mol ratio of ether, the Grubbs catalyst and the terminator is 1:100.
7. according to the method described in claim 1, it is characterised in that in the step 2 and the step 3, it is described the first
Organic solvent or second of organic solvent are dichloromethane, chloroform, acetone, methanol, tetrahydrofuran, N, N- dimethyl
Any one in formamide, dimethyl sulfoxide (DMSO) and DMAC N,N' dimethyl acetamide.
8. according to the method described in claim 1, it is characterised in that in the step 4, the nitrine reagent and the poly- drop
The chain link mol ratio of bornylene bis-mesylate is (1:1)~(20:1)；
The nitrine reagent is sodium azide, Lithium Azide or tetrabutyl ammonium azide；
The third described solvent is N,N-dimethylformamide or dimethyl sulfoxide (DMSO).
9. the nitrine with polynorbornene backbone structure prepared by a kind of method according to described in the claims 1~8 gathers
Compound, it is characterised in that the azide polymer with polynorbornene backbone structure has said structure formula (IV).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503795A (en) * | 2018-04-19 | 2018-09-07 | 西安近代化学研究所 | Crosslinked glycidyl azide polymer of triazoline key and preparation method thereof |
| CN109400852A (en) * | 2018-11-09 | 2019-03-01 | 天津大学 | A kind of organic polymer and preparation method based on anthraquinone and the application as anode material for lithium-ion batteries |
| CN112094399A (en) * | 2019-06-18 | 2020-12-18 | 中国科学院福建物质结构研究所 | Polymer containing azide and preparation method thereof |
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| CN102180755A (en) * | 2011-03-16 | 2011-09-14 | 清华大学 | Synthesis method of azide compounds |
| CN103880704A (en) * | 2014-03-21 | 2014-06-25 | 南京理工大学 | Azide ester compound, synthetic method and application of compound |
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| CN102180755A (en) * | 2011-03-16 | 2011-09-14 | 清华大学 | Synthesis method of azide compounds |
| CN103880704A (en) * | 2014-03-21 | 2014-06-25 | 南京理工大学 | Azide ester compound, synthetic method and application of compound |
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| 董婕: "《端叠氮基聚丁二烯的合成与应用研究》", 31 July 2015 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503795A (en) * | 2018-04-19 | 2018-09-07 | 西安近代化学研究所 | Crosslinked glycidyl azide polymer of triazoline key and preparation method thereof |
| CN108503795B (en) * | 2018-04-19 | 2020-10-27 | 西安近代化学研究所 | Triazoline bond crosslinked poly-azido glycidyl ether and preparation method thereof |
| CN109400852A (en) * | 2018-11-09 | 2019-03-01 | 天津大学 | A kind of organic polymer and preparation method based on anthraquinone and the application as anode material for lithium-ion batteries |
| CN112094399A (en) * | 2019-06-18 | 2020-12-18 | 中国科学院福建物质结构研究所 | Polymer containing azide and preparation method thereof |
| CN112094399B (en) * | 2019-06-18 | 2021-05-11 | 中国科学院福建物质结构研究所 | Polymer containing azide and preparation method thereof |
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| CN107312114B (en) | 2020-11-13 |
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