CN117603455A - Polycarbonate block copolymer quaternary ammonium salt and preparation method thereof - Google Patents
Polycarbonate block copolymer quaternary ammonium salt and preparation method thereof Download PDFInfo
- Publication number
- CN117603455A CN117603455A CN202311751264.6A CN202311751264A CN117603455A CN 117603455 A CN117603455 A CN 117603455A CN 202311751264 A CN202311751264 A CN 202311751264A CN 117603455 A CN117603455 A CN 117603455A
- Authority
- CN
- China
- Prior art keywords
- block copolymer
- quaternary ammonium
- ammonium salt
- polycarbonate
- polycarbonate block
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 83
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 83
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 75
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- 239000002879 Lewis base Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 9
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002841 Lewis acid Substances 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 106
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000002244 precipitate Substances 0.000 claims description 34
- 239000012043 crude product Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 9
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 5
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- -1 carboxyl compound Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 3
- 229940073608 benzyl chloride Drugs 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 3
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 claims description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 2
- LKOYNWCKHRXSKP-UHFFFAOYSA-N 2-(1-ethoxyethoxymethyl)oxirane Chemical compound CCOC(C)OCC1CO1 LKOYNWCKHRXSKP-UHFFFAOYSA-N 0.000 claims description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- LLZMVRSUOWXPTP-UHFFFAOYSA-N benzyl oxirane-2-carboxylate Chemical compound C1OC1C(=O)OCC1=CC=CC=C1 LLZMVRSUOWXPTP-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- 239000011630 iodine Chemical group 0.000 claims description 2
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011968 lewis acid catalyst Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 2
- YLNSNVGRSIOCEU-UHFFFAOYSA-N oxiran-2-ylmethyl butanoate Chemical compound CCCC(=O)OCC1CO1 YLNSNVGRSIOCEU-UHFFFAOYSA-N 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
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 19
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 54
- 239000001569 carbon dioxide Substances 0.000 description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- DZFGVGDQHQHOKZ-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C(O)=O DZFGVGDQHQHOKZ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- VVTWGRISPKCUQA-UHFFFAOYSA-N 4-benzylsulfanyl-4-sulfanylidenebutanoic acid Chemical compound C1(=CC=CC=C1)CSC(=S)CCC(=O)O VVTWGRISPKCUQA-UHFFFAOYSA-N 0.000 description 2
- YPCMISLZCVOUJB-UHFFFAOYSA-N 4-cyano-4-methyl-5-phenyl-5-sulfanylidenepentanoic acid Chemical compound OC(=O)CCC(C)(C#N)C(=S)C1=CC=CC=C1 YPCMISLZCVOUJB-UHFFFAOYSA-N 0.000 description 2
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 231100000783 metal toxicity Toxicity 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- XDMFYOPNYBTJLJ-UHFFFAOYSA-N n-bromobutan-1-amine Chemical compound CCCCNBr XDMFYOPNYBTJLJ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/183—Block or graft polymers containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of polymer synthesis, and discloses a polycarbonate block copolymer quaternary ammonium salt and a preparation method thereof. CO is reacted with a nonmetallic Lewis acid and a Lewis base catalyst by using a difunctional chain transfer agent 2 The epoxy monomer and the olefin monomer are copolymerized to prepare the polycarbonate block copolymer by a one-step method, and the copolymer is further quaternized to obtain the polycarbonate block copolymer quaternary ammonium salt. The invention has the beneficial effects that: the polymer obtained is free of residual metals and nontoxic by using a non-metallic Lewis acid/Lewis base catalyst; the block copolymer is polymerized by adopting a one-step method, so that the preparation efficiency is improved and the preparation cost is reduced compared with the traditional two-step method; the method for introducing the quaternary ammonium salt by constructing the block copolymer can avoid the synthesis of the epoxy monomer with the modifiable group, and simultaneously can prepare the quaternary ammonium salt precursor polymer in one step, thereby improving the preparation efficiency compared with the traditional method for introducing the quaternary ammonium salt by modifying the side chain of the polycarbonate.
Description
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a polycarbonate block copolymer quaternary ammonium salt and a preparation method thereof.
Background
Carbon dioxide (CO) 2 ) Is a main greenhouse gas and is also a cheap carbon-oxygen resource. By CO 2 Can synthesize basic chemicals, energy chemicals and high molecular materials, wherein, CO is used as 2 And epoxide as raw materials, and the copolymerization of polycarbonate under the action of catalyst is the most promising CO 2 The synthesized polycarbonate is a degradable high polymer material, has good transparency and excellent oxygen and water blocking performance, and can be applied to the fields of engineering plastics, disposable medicines, food packaging materials, adhesives and the like.
CO at present 2 Base polycarbonates have certain disadvantages. On the one hand, the production cost is high, and most of the used catalysts are expensive metal catalysts; on the other hand, CO 2 The base polycarbonate also has certain performance defects, such as poor thermal stability and poor mechanical properties; these drawbacks limit CO to some extent 2 Large scale application of base polycarbonates. The block copolymer contains two or more polymer sequence structures with different properties, has the excellent properties of multiple polymers, can overcome the defect of a single polymer material, or can endow the single polymer material with new functions.
The traditional synthesis of the segmented copolymer mainly adopts a multi-step method, needs step feeding and indirect purification, and has the disadvantages of complex polymerization process, time and labor waste and higher production cost. Meanwhile, some polycarbonate block copolymers require metal catalysts for their synthesis, which are difficult to remove completely from the block copolymer, and the residual metal often contaminates the polymer with the color of the metal or imparts some toxicity to the polymer.
The quaternary ammonium salt is a good antibacterial molecule and is widely applied to the field of antibacterial materials. The polycarbonate itself has no antibacterial property, and the quaternary ammonium salt molecules are connected to the polycarbonate through chemical bonds by a certain preparation method, so that the antibacterial property of the polycarbonate can be endowed. The side chain modification of polycarbonate is a common means by three steps including synthesis of polycarbonate, synthesis of quaternary ammonium salt and side chain modification of polycarbonate. Among them, in addition to the conventional epoxide, the epoxide containing a post-modifiable group (such as double bond) which is synthesized in advance is required to be used in the synthesis of the polycarbonate, and the synthesis steps are complicated.
In view of the above, there is a need to develop a new method for synthesizing quaternary ammonium salts of polycarbonate block copolymers, which is simple in steps, uses a relatively environmentally friendly catalytic system, and can simultaneously impart diversified structures to the polymer.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polycarbonate segmented copolymer quaternary ammonium salt and a preparation method thereof; in the polycarbonate block copolymer quaternary ammonium salt, the quaternary ammonium salt and the polycarbonate are respectively positioned on two different blocks; the preparation method of the polycarbonate block copolymer quaternary ammonium salt has the advantages of simple preparation steps, mild reaction conditions, low toxicity and low cost, and good application prospect.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a polycarbonate block copolymer quaternary ammonium salt and a preparation method thereof, wherein the polycarbonate block copolymer quaternary ammonium salt has a structure shown in a formula (I) or (II):
the number average molecular weight of the polycarbonate segmented copolymer quaternary ammonium salt is 500-100000, and the molecular weight distribution is 1.01-3.30;
z is selected from formula a or formula b:
the R is 5 Selected from C2-C12 alkyl or benzyl;
R 1 selected from formulas c-g:
R 2 selected from the formula h-k:
R 3 selected from hydrogen, halogen, C1-C12 aliphatic, C1-C12 substituted aliphatic, C2-C18 substituted hetero aliphatic containing oxygen or silicon atoms, aryl, substituted aryl;
R 4 selected from hydrogen, vinyl;
R 6 selected from propyl, n-butyl, benzyl;
x is selected from chlorine, bromine and iodine;
x is 1-99%, y is 1-99%, z is 0-50%, and x+y+z=1;
in the formulae a to k, the broken line represents the substitution position.
The invention provides a preparation method of a polycarbonate block copolymer quaternary ammonium salt, which comprises the following steps:
(1) Under the anhydrous and anaerobic condition, mixing an epoxy monomer, an olefin monomer, a bifunctional chain transfer agent, a nonmetallic Lewis acid catalyst and a nonmetallic Lewis base catalyst to obtain a raw material mixture;
(2) Adding the raw material mixture obtained in the step (1) into a pressure-resistant reactor, and introducing CO with the pressure of 0.1-5 MPa 2 Then sealing the reactor, heating to 30-120 ℃, continuously reacting for 1-72 hours, cooling to room temperature, releasing pressure to obtain a crude product, dissolving the crude product by adopting an organic solvent to obtain a block copolymer solution, further adding the block copolymer solution into a precipitator for precipitation, separating out precipitate, and drying to obtain a polycarbonate block copolymer;
(3) Dissolving the polycarbonate block copolymer and haloalkane in an organic solvent (the concentration of the polycarbonate block copolymer is 0.05-0.5 g/mL under the nitrogen environment, heating the system to 50-120 ℃, reacting for 1-72 hours, cooling to room temperature after the reaction is finished, rotationally evaporating to remove the solvent to obtain a crude product of the quaternary ammonium salt, dissolving the crude product with the organic solvent to obtain a quaternary ammonium salt solution, adding the quaternary ammonium salt solution into a precipitator for precipitation, separating out precipitate, and drying to obtain the quaternary ammonium salt of the polycarbonate block copolymer.
Preferably, the polymerization is carried out under anhydrous and anaerobic conditions, with a water content of 80ppm or less.
Preferably, the epoxy monomer in step (1) is one or more of ethylene oxide, propylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, styrene oxide, 1, 2-butylene oxide, 4-hydroxymethyl cyclohexane oxide, allyl glycidyl ether, benzyl glycidate, glycidyl butyrate, 2- ((1-ethoxyethoxy) methyl) ethylene oxide, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane.
Preferably, the olefin monomer in the step (1) is one or more of 4-vinyl pyridine, 2-vinyl pyridine, 1-vinyl imidazole, dimethylaminoethyl methacrylate and N, N-dimethylacrylamide.
Preferably, the molar ratio of the epoxy monomer to the olefin monomer in the step (1) is 100:1-1:100.
Preferably, the difunctional chain transfer agent in step (1) is a terminal carboxyl compound, and the difunctional chain transfer agent also comprises a disulfide bond or a trithiobond. More preferably, the difunctional chain transfer agent is one of 2- [ dodecylthio (thiocarbonyl) thio ] -2-methylpropanoic acid, 4-cyano-4- (thiobenzoyl) pentanoic acid, 4-cyano-4- (dodecylthio-thiocarbonyl) thiolanoic acid, 3-benzylmercapto-thiocarbonyl propionic acid.
Preferably, the molar ratio of the difunctional chain transfer agent to the epoxy monomer is from 1:10 to 1:1000.
Preferably, the nonmetallic lewis acid in step (1) is one of triethylborane, triphenylborane, and tris (pentafluorophenyl) borane.
Preferably, the molar ratio of the nonmetallic Lewis acid to the epoxy monomer is 1:1000-1:50.
Preferably, the nonmetallic Lewis base of step (1) is one of 4-dimethylaminopyridine, triethylamine, triphenylphosphine, bis (triphenylphosphine) ammonium chloride, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene, 1, 8-diazabicyclo (5.4.0) undec-7-ene.
Preferably, the molar ratio of the nonmetallic Lewis base to the epoxy monomer is 1:1000-1:50.
Preferably, the CO of step (2) 2 The pressure is 0.5 to 4MPa, more preferably 1 to 3MPa.
Preferably, the reaction temperature in the step (2) is 40-100 ℃.
Preferably, the reaction time in the step (2) is 12-48 h.
Preferably, the organic solvent in the step (2) is one or more of dichloromethane, ethyl acetate, tetrahydrofuran and acetone.
Preferably, the precipitant in the step (2) is one or more of diethyl ether, petroleum ether, n-hexane, methanol and ethanol.
Preferably, the haloalkane in the step (3) is one or more of chloropropane, bromopropane, iodopropane, chloro-n-butane, bromo-n-butane, iodo-n-butane, chlorotoluene, benzyl chloride, benzyl bromide and benzyl iodide.
Preferably, the molar ratio of the polycarbonate block copolymer to the haloalkane in the step (3) is 1:1 to 1:200.
Preferably, the organic solvent in the step (3) is one or more of toluene, tetrahydrofuran, methanol, ethanol and acetonitrile.
Preferably, the precipitant in the step (3) is one or more of diethyl ether, petroleum ether, n-hexane, methanol and ethanol.
Compared with the prior art, the invention has the following advantages:
the invention successfully utilizes CO 2 And (3) preparing a polycarbonate block copolymer by copolymerizing an epoxy monomer and an olefin monomer through a one-step method, and further quaternizing the polycarbonate block copolymer to obtain the polycarbonate block copolymer quaternary ammonium salt. In the block copolymer quaternary ammonium salt, the quaternary ammonium salt and the polycarbonate are positioned in different blocks, so that the excellent performance of the different blocks can be fully exerted; the type and the proportion of the quaternary ammonium salt can be regulated by controlling the reaction feeding.
The non-metal Lewis acid/Lewis base catalyst used in the method for synthesizing the block copolymer quaternary ammonium salt is simple and easy to obtain, and the obtained polymer has no residual metal and no toxicity and has potential of application in the field of biological medicine.
Compared with the traditional preparation of the block copolymer by a two-step method, the method only needs one feeding, is simple to operate, improves the preparation efficiency and reduces the preparation cost.
Compared with the traditional method for introducing quaternary ammonium salt through modification of polycarbonate side chains, the method for introducing quaternary ammonium salt through construction of the block copolymer, which is used in the invention, can avoid synthesis of epoxy monomers with modifiable groups, and simultaneously can prepare the quaternary ammonium salt precursor polymer in one step, thereby greatly improving the preparation efficiency.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a polycarbonate block copolymer in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a quaternary ammonium salt of the polycarbonate block copolymer in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, which are not to be construed as limiting the scope of the invention. The various raw materials of the present invention may be obtained commercially unless specifically stated; or prepared according to methods conventional in the art. Unless defined or otherwise indicated, the terms of art used in the present invention have the same meaning as those skilled in the art.
Example 1
Epoxycyclohexane (9.8 g,0.1mol,200.0 eq.) 2-vinylpyridine (5.25 g,0.05mol,100.0 eq.) 2- [ dodecylthio (thiocarbonyl) thio]2-Methylpropionic acid (365 mg,1mmol,2.0 eq.) triethylboron (0.5 mL of 1.0mol/L TEB in THF,0.5mmol,1.0 eq.) and bis (triphenylphosphine) ammonium chloride (144 mg,0.25mmol,0.5 eq.) were charged into a 50mL autoclave previously subjected to dehydration and oxygen removal treatment, and 1MPa CO was introduced thereinto 2 The reaction vessel was then closed, the temperature of the reaction vessel was raised to 80℃and the reaction was continued with stirring at that temperature for 24 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and CO is released 2 The crude product was obtained, and 10mL of methylene chloride was used to dissolve the crude product to obtain a block copolymer solution, which was added to 100mL of petroleum ether to precipitate, the precipitate was separated, and the precipitate was washed twice with petroleum ether, and dried to obtain a polycarbonate block copolymer. The nuclear magnetic resonance hydrogen spectrum of the polycarbonate segmented copolymer is characterized as shown in figure 1, wherein characteristic peaks with chemical shift of 6.0-8.5ppm are attributed to hydrogen on pyridine in poly-2-vinyl pyridine, and characteristic peaks with chemical shift of 4.5-4.8ppm are attributed to hydrogen of methine connected with carbonate bonds in polycarbonate.
Reacting 5g of polycarbonate block copolymer with 2g of n-butylamine bromide in 20mL of methanol under nitrogen environment at 60 ℃ for 72 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude quaternary ammonium salt product; the crude product was dissolved with 5mL of methylene chloride to obtain a quaternary ammonium salt solution, which was added to 50mL of petroleum ether for precipitation, the precipitate was separated, the precipitate was washed twice with petroleum ether, and 5.6g of a quaternary ammonium salt of a polycarbonate block copolymer was obtained after drying. The number average molecular weight of this polymer was 8.9kg/mol as determined by gel permeation chromatography and the molecular weight distribution was 1.28. The quaternary ammonium salt was subjected to nuclear magnetic hydrogen spectrum characterization as shown in fig. 2. In contrast to FIG. 1, the integral area of the characteristic peaks for chemical shifts 3.4-3.5ppm and 1.0-2.0ppm increases, corresponding to the characteristic peaks for methyl and methylene groups of n-butane on the quaternary ammonium salt.
Example 2
Propylene oxide (5.8 g,0.1mol,200.0 eq.), 4-vinylpyridine (10.5 g,0.1mol,200.0 eq.), 4-cyano-4- (thiobenzoyl) pentanoic acid (279 mg,1mmol,2.0 eq.), triethylboron (0.5 mL of 1.0mol/L TEB in THF,0.5mmol,1.0 eq.) and bis (triphenylphosphine) ammonium chloride (2877 mg,0.5mmol,1.0 eq.) were charged into a 50mL autoclave which had been previously dehydrated and deoxygenated, and 1.5MPa CO was introduced 2 The reaction vessel was then closed, the temperature of the reaction vessel was raised to 70℃and the reaction was continued with stirring at that temperature for 24 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and CO is released 2 A crude product was obtained, and the crude product was dissolved with 10mL of methylene chloride to obtain a block copolymer solution, which was added to 100mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and the polycarbonate block copolymer was obtained after drying. And the polycarbonate is subjected to nuclear magnetic hydrogen spectrum characterization, so that the structure is correct.
Reacting 5g of polycarbonate block copolymer with 2.5g of bromo-n-butylamine in 20mL of methanol under nitrogen at 60 ℃ for 72 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude quaternary ammonium salt product; the crude product was dissolved with 5mL of methylene chloride to obtain a quaternary ammonium salt solution, which was added to 50mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and 5.9g of a quaternary ammonium salt of a polycarbonate block copolymer was obtained after drying. The number average molecular weight of this polymer was 11.1kg/mol as determined by gel permeation chromatography and the molecular weight distribution was 1.35.
Example 3
Cycloepoxyhexane (9.8 g,0.1mol,200.0 eq.) dimethylaminoethyl methacrylate (7.85 g,0.05mol,100.0 eq.) 2- [ dodecylthio (thiocarbonyl) thio ]]-2-methyl groupPropionic acid (365 mg,1mmol,2.0 eq.) triethylboron (0.5 mL of 1.0mol/L TEB in THF,0.5mmol,1.0 eq.) and 1, 8-diazabicyclo (5.4.0) undec-7-ene (76 mg,0.5mmol,1.0 eq.) were added to a 50mL autoclave which had been previously dehydrated and deoxygenated, and 1MPa CO was introduced 2 The reaction vessel was then closed, the temperature of the reaction vessel was raised to 80℃and the reaction was continued with stirring at that temperature for 24 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and CO is released 2 A crude product was obtained, and the crude product was dissolved with 10mL of tetrahydrofuran to obtain a block copolymer solution, which was added to 100mL of diethyl ether for precipitation, the precipitate was separated, and the precipitate was washed twice with diethyl ether and dried to obtain a polycarbonate block copolymer. And the polycarbonate is subjected to nuclear magnetic hydrogen spectrum characterization, so that the structure is correct.
Reacting 5g of polycarbonate block copolymer with 2g of n-butylamine bromide in 20mL of methanol under nitrogen environment at 60 ℃ for 24 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude quaternary ammonium salt product; the crude product was dissolved with 5mL of tetrahydrofuran to obtain a quaternary ammonium salt solution, which was added to 50mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and 5.8g of a quaternary ammonium salt of a polycarbonate block copolymer was obtained after drying. The number average molecular weight of this polymer was 8.6kg/mol as determined by gel permeation chromatography and the molecular weight distribution was 1.40.
Example 4
Cycloepoxyhexane (9.8 g,0.1mol,500.0 eq.) dimethylaminoethyl methacrylate (3.14 g,0.02mol,100.0 eq.) 2- [ dodecylthio (thiocarbonyl) thio ]]2-methylpropanoic acid (146 mg,0.4mmol,2.0 eq.) triethylboron (0.2 mL of 1.0mol/L TEB in THF,0.2mmol,1.0 eq.) and bis (triphenylphosphine) ammonium chloride (57 mg,0.1mmol,0.5 eq.) were added to a 50mL autoclave which had been previously dehydrated and deoxygenated, and 3MPa CO was introduced 2 The reaction vessel was then closed, heated to 90℃and stirred continuously at this temperature for 12 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and CO is released 2 To obtain a crude product, dissolving the crude product with 10mL of methylene chloride to obtain a block copolymer solution, adding the block copolymer solution into 100mL of diethyl ether for precipitation, and separating out the precipitateThe resultant was washed with diethyl ether to precipitate twice, and dried to obtain a polycarbonate block copolymer. And the polycarbonate is subjected to nuclear magnetic hydrogen spectrum characterization, so that the structure is correct.
Reacting 5g of polycarbonate block copolymer with 3g of benzyl bromide in 20mL of methanol under nitrogen environment at 60 ℃ for 48 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude quaternary ammonium salt product; the crude product was dissolved with 5mL of methylene chloride to obtain a quaternary ammonium salt solution, which was added to 50mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and 5.5g of a quaternary ammonium salt of a polycarbonate block copolymer was obtained after drying. The number average molecular weight of this polymer was 14.8kg/mol and the molecular weight distribution was 1.15 as determined by gel permeation chromatography.
Example 5
Epoxycyclohexane (9.8 g,0.1mol,100 eq.) 2-vinylpyridine (5.25 g,0.05mol,50 eq.) 2- [ dodecylthio (thiocarbonyl) thio]2-methylpropanoic acid (146 mg,0.4mmol,0.4 eq.), triphenylborane (242 mg,1mmol,1 eq.) and bis (triphenylphosphine) ammonium chloride (574 mg,1mmol,1 eq.) were charged into a 50mL autoclave previously dehydrated and deoxygenated, and 2.5MPa CO was introduced 2 The reaction vessel was then closed, the reaction vessel was warmed to 90℃and stirred continuously at this temperature for 24 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and CO is released 2 A crude product was obtained, and the crude product was dissolved with 10mL of methylene chloride to obtain a block copolymer solution, which was added to 100mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and the polycarbonate block copolymer was obtained after drying. And the polycarbonate is subjected to nuclear magnetic hydrogen spectrum characterization, so that the structure is correct.
Reacting 5g of polycarbonate block copolymer with 3g of benzyl chloride in 40mL of ethanol under a nitrogen environment at the temperature of 75 ℃ for 48 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude quaternary ammonium salt product; the crude product was dissolved with 5mL of methylene chloride to obtain a quaternary ammonium salt solution, which was added to 50mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and 5.4g of a quaternary ammonium salt of a polycarbonate block copolymer was obtained after drying. The number average molecular weight of this polymer was 6.3kg/mol and the molecular weight distribution was 1.24 as determined by gel permeation chromatography.
Example 6
Propylene oxide (5.8 g,0.1mol,200 eq.), 1-vinylimidazole (4.7 g,0.05mol,100 eq.), 3-benzylmercaptothiocarbonylpropionic acid (109 mg,0.4mmol,0.8 eq.), triethylboron (0.5 mL of 1.0mol/L TEB in THF,0.5mmol,1.0 eq.), bis (triphenylphosphine) ammonium chloride (287 mg,0.5mmol,1.0 eq.) were charged to a 50mL autoclave which had been dehydrated and deoxygenated beforehand, and 1.5MPa CO was introduced 2 The reaction vessel was then closed, heated to 60℃and allowed to react with stirring for 72 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and CO is released 2 A crude product was obtained, and the crude product was dissolved with 10mL of methylene chloride to obtain a block copolymer solution, which was added to 100mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and the polycarbonate block copolymer was obtained after drying. And the polycarbonate is subjected to nuclear magnetic hydrogen spectrum characterization, so that the structure is correct.
Reacting 5g of polycarbonate block copolymer with 3g of n-butyl chloride in 20mL of methanol under nitrogen at 60 ℃ for 48 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude quaternary ammonium salt product; the crude product was dissolved with 5mL of methylene chloride to obtain a quaternary ammonium salt solution, which was added to 50mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and 5.2g of a quaternary ammonium salt of a polycarbonate block copolymer was obtained after drying. The number average molecular weight of this polymer was 6.8kg/mol as determined by gel permeation chromatography and the molecular weight distribution was 1.26.
Example 7
2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (12.3 g,0.05mol,100 eq.) 2-vinylpyridine (2.63 g,0.025mol,50 eq.) 2- [ dodecylthio (thiocarbonyl) thio]2-methylpropanoic acid (73 mg,0.2mmol,0.4 eq.) triethylboron (0.5 mL of 1.0mol/L TEB in THF,0.5mmol,1.0 eq.) and bis (triphenylphosphine) ammonium chloride (287 mg,0.5mmol,1.0 eq.) were added to a 50mL autoclave which had been previously dehydrated and deoxygenated, and 1MPa CO was introduced 2 Sealing the reaction kettle, heating the reaction kettle to 55 ℃, and heating the reaction kettle at the temperature ofThe reaction was stirred continuously at this temperature for 72 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and CO is released 2 A crude product was obtained, and the crude product was dissolved with 10mL of methylene chloride to obtain a block copolymer solution, which was added to 100mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and the polycarbonate block copolymer was obtained after drying. And the polycarbonate is subjected to nuclear magnetic hydrogen spectrum characterization, so that the structure is correct.
Reacting 5g of polycarbonate block copolymer with 3g of bromo-n-butane in 10mL of methanol under nitrogen at 60 ℃ for 48 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude quaternary ammonium salt product; the crude product was dissolved with 5mL of methylene chloride to obtain a quaternary ammonium salt solution, which was added to 50mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and 5.4g of a quaternary ammonium salt of a polycarbonate block copolymer was obtained after drying. The number average molecular weight of this polymer was 9.3kg/mol as determined by gel permeation chromatography and the molecular weight distribution was 1.32.
Example 8
1, 2-epoxybutane (7.2 g,0.1mol,100 eq.) 4-vinylpyridine (10.5 g,0.1mol,100 eq.) 2- [ dodecylthio (thiocarbonyl) thio]2-methylpropanoic acid (73 mg,0.2mmol,0.2 eq.), triethylboron (1 mL of 1.0mol/L of TEB in THF,1mmol,1.0 eq.) and triphenylphosphine (262 mg,1mmol,1.0 eq.) were charged into a 50mL autoclave previously dehydrated and deoxygenated, and 2MPa CO was introduced 2 The reaction vessel was then closed, heated to 50℃and allowed to react at that temperature with continuous stirring for 48 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and CO is released 2 A crude product was obtained, and the crude product was dissolved with 10mL of methylene chloride to obtain a block copolymer solution, which was added to 100mL of n-hexane for precipitation, the precipitate was separated, and the precipitate was washed twice with n-hexane, and dried to obtain a polycarbonate block copolymer. And the polycarbonate is subjected to nuclear magnetic hydrogen spectrum characterization, so that the structure is correct.
Reacting 5g of polycarbonate block copolymer with 3g of bromo-n-butane in 10mL of methanol under nitrogen at 60 ℃ for 72 hours, cooling to room temperature, and removing the solvent by rotary evaporation to obtain a crude quaternary ammonium salt product; the crude product was dissolved with 5mL of methylene chloride to obtain a quaternary ammonium salt solution, which was added to 50mL of diethyl ether for precipitation, the precipitate was separated, the precipitate was washed twice with diethyl ether, and 5.3g of a quaternary ammonium salt of a polycarbonate block copolymer was obtained after drying. The number average molecular weight of this polymer was 8.4kg/mol as determined by gel permeation chromatography and the molecular weight distribution was 1.25.
Claims (8)
1. A quaternary ammonium salt of a polycarbonate block copolymer, characterized in that the quaternary ammonium salt of a polycarbonate block copolymer has a structure represented by formula (I) or (II):
the number average molecular weight of the polycarbonate segmented copolymer quaternary ammonium salt is 500-100000, and the molecular weight distribution is 1.01-3.30;
z is selected from formula a or formula b:
the R is 5 Selected from C2-C12 alkyl or benzyl;
R 1 selected from formulas c-g:
R 2 selected from the formula h-k:
R 3 selected from hydrogen, halogenA C1-C12 aliphatic group, a C1-C12 substituted aliphatic group, a C2-C18 substituted heteroaliphatic group containing an oxygen or silicon atom, an aryl group, a substituted aryl group;
R 4 selected from hydrogen, vinyl;
R 6 selected from propyl, n-butyl, benzyl; x is selected from chlorine, bromine and iodine;
x is 1-99%, y is 1-99%, z is 0-50%, and x+y+z=1;
the dashed lines in formulas a-k represent substitution positions.
2. A preparation method of a polycarbonate block copolymer quaternary ammonium salt is characterized by comprising the following steps:
(1) Under the anhydrous and anaerobic condition, mixing an epoxy monomer, an olefin monomer, a bifunctional chain transfer agent, a nonmetallic Lewis acid catalyst and a nonmetallic Lewis base catalyst to obtain a raw material mixture;
(2) Adding the raw material mixture obtained in the step (1) into a pressure-resistant reactor, and introducing CO with the pressure of 0.1-5 MPa 2 Then sealing the reactor, heating to 30-120 ℃, continuously reacting for 1-72 hours, cooling to room temperature, releasing pressure to obtain a crude product, dissolving the crude product by adopting an organic solvent to obtain a block copolymer solution, further adding the block copolymer solution into a precipitator for precipitation, separating out precipitate, and drying to obtain a polycarbonate block copolymer;
(3) Dissolving the polycarbonate block copolymer and haloalkane in an organic solvent (the concentration of the polycarbonate block copolymer is 0.05-0.5 g/mL), heating the system to 50-120 ℃ in a nitrogen environment, reacting for 1-72 hours, cooling to room temperature after the reaction is finished, rotationally evaporating to remove the solvent to obtain a crude product of the quaternary ammonium salt, dissolving the crude product with the organic solvent to obtain a quaternary ammonium salt solution, adding the quaternary ammonium salt solution into a precipitator for precipitation, separating out precipitate, and drying to obtain the quaternary ammonium salt of the polycarbonate block copolymer.
3. The method of claim 2, wherein the epoxy monomer of step (1) is one or more of ethylene oxide, propylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, styrene oxide, 1, 2-butylene oxide, 4-methylol cyclohexane oxide, allyl glycidyl ether, benzyl glycidate, glycidyl butyrate, 2- ((1-ethoxyethoxy) methyl) ethylene oxide, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; the olefin monomer is one or more of 4-vinyl pyridine, 2-vinyl pyridine, 1-vinyl imidazole, dimethylaminoethyl methacrylate and N, N-dimethyl acrylamide; the molar ratio of the epoxy monomer to the olefin monomer is 100:1-1:100.
4. The process according to claim 2, wherein the bifunctional chain transfer agent of step (1) is a terminal carboxyl compound, and comprises a disulfide bond or a trithiobond; the molar ratio of the difunctional chain transfer agent to the epoxy monomer in the step (1) is 1:10-1:1000.
5. The method of claim 2, wherein the nonmetallic lewis acid of step (1) is one of triethylborane, triphenylborane, and tris (pentafluorophenyl) borane;
the nonmetallic Lewis base is one of 4-dimethylaminopyridine, triethylamine, triphenylphosphine, bis (triphenylphosphine) ammonium chloride, 1,5, 7-triazidine (4.4.0) dec-5-ene and 1, 8-diazabicyclo (5.4.0) undec-7-ene;
the molar ratio of the nonmetallic Lewis acid to the epoxy monomer is 1:1000-1:50, and the molar ratio of the nonmetallic Lewis base to the epoxy monomer is 1:1000-1:50.
6. The method according to claim 2, wherein the organic solvent in the step (2) is one or more of dichloromethane, ethyl acetate, tetrahydrofuran and acetone; the precipitant is one or more of diethyl ether, petroleum ether, n-hexane, methanol and ethanol.
7. The preparation method of claim 2, wherein the haloalkane in the step (3) is one or more of chloropropane, bromopropane, iodopropane, chloro-n-butane, bromo-n-butane, iodo-n-butane, chlorotoluene, benzyl chloride, benzyl bromide and benzyl iodide; the molar ratio of the polycarbonate segmented copolymer to the haloalkane is 1:1-1:200.
8. The preparation method of claim 2, wherein the organic solvent in the step (3) is one or more of toluene, tetrahydrofuran, methanol, ethanol and acetonitrile; the precipitant is one or more of diethyl ether, petroleum ether, n-hexane, methanol and ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311751264.6A CN117603455A (en) | 2023-12-19 | 2023-12-19 | Polycarbonate block copolymer quaternary ammonium salt and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311751264.6A CN117603455A (en) | 2023-12-19 | 2023-12-19 | Polycarbonate block copolymer quaternary ammonium salt and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117603455A true CN117603455A (en) | 2024-02-27 |
Family
ID=89953559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311751264.6A Pending CN117603455A (en) | 2023-12-19 | 2023-12-19 | Polycarbonate block copolymer quaternary ammonium salt and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117603455A (en) |
-
2023
- 2023-12-19 CN CN202311751264.6A patent/CN117603455A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108774256B (en) | Preparation method of oligomeric multicenter metalloporphyrin complex and polycarbonate | |
| CN109988290B (en) | Preparation method of oligomeric metalloporphyrin complex and polycarbonate | |
| CN108752575B (en) | Preparation method of polyester material | |
| CN103333329A (en) | Method for preparing polycarbonate by copolymerizing carbon dioxide and alpha-pinene derivatives | |
| CN108409954A (en) | A kind of synthetic method of carbon dioxide-base polycarbonate block copolymer | |
| CN115304577B (en) | Preparation method of vinylene carbonate | |
| CN113929813B (en) | Multifunctional metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate | |
| CN117157342A (en) | Polypropylene lactone and preparation method | |
| CN111925400B (en) | Redox-responsive metalloporphyrin complex, preparation method thereof and preparation method of polylactic acid | |
| CN117603455A (en) | Polycarbonate block copolymer quaternary ammonium salt and preparation method thereof | |
| CN114891194B (en) | Double-functional polymer catalyst for synthesizing polyester and application thereof | |
| EP3645601A1 (en) | Cyclobutane-1, 3-diacid building blocks | |
| JP4136886B2 (en) | Polymers of novel alicyclic vinyl ethers | |
| CN104592425B (en) | A kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application | |
| CN115353836B (en) | Sulfur-containing octanoic acid anion terpolymer adhesive and preparation method thereof | |
| CN114891035A (en) | Difunctional tetranuclear metal lithium complex and preparation method and application thereof | |
| Endo et al. | A Novel Crosslinking-Decrosslinking System of Polymers Having Spiro Orthoester Moieties in the Side Chains. | |
| KR101767310B1 (en) | Method for synthesizing terpolymer of epoxide containing electon withdrawing group, CO2 and epoxide non-contaning electon withdrawing group | |
| CN110256636B (en) | Aliphatic polycarbonate-g-polystyrene graft polymer and preparation method thereof | |
| CN114560964A (en) | Synthetic method and application of carboxyl functional polyion liquid | |
| CN109293810B (en) | Controllable free radical polymerization method catalyzed by nonmetal | |
| CN117843649A (en) | Difunctional multi-center metalloporphyrin complex and application thereof in preparation of polycarbonate | |
| CN111171205B (en) | Production method of polypropylene | |
| CN117903149A (en) | Metalloporphyrin complex and application thereof in catalytic preparation of polyether | |
| CN115838453B (en) | Polymer heteronuclear porphyrin complex and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |