WO2024130673A1 - Polymer and preparation method therefor - Google Patents
Polymer and preparation method therefor Download PDFInfo
- Publication number
- WO2024130673A1 WO2024130673A1 PCT/CN2022/141241 CN2022141241W WO2024130673A1 WO 2024130673 A1 WO2024130673 A1 WO 2024130673A1 CN 2022141241 W CN2022141241 W CN 2022141241W WO 2024130673 A1 WO2024130673 A1 WO 2024130673A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- solvent
- polymer
- reaction
- mol
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- 239000002904 solvent Substances 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000012298 atmosphere Substances 0.000 claims abstract description 21
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 90
- 150000001875 compounds Chemical class 0.000 claims description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 52
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 51
- 238000010791 quenching Methods 0.000 claims description 46
- 230000000171 quenching effect Effects 0.000 claims description 46
- 239000003153 chemical reaction reagent Substances 0.000 claims description 43
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 18
- -1 poly(N,N-dimethylacrylamide) Polymers 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 150000002825 nitriles Chemical class 0.000 claims description 13
- 239000004627 regenerated cellulose Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000011026 diafiltration Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 6
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 125000004043 oxo group Chemical group O=* 0.000 claims description 2
- 229920000765 poly(2-oxazolines) Polymers 0.000 claims description 2
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 27
- 238000003786 synthesis reaction Methods 0.000 abstract description 27
- 238000004260 weight control Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- 239000002994 raw material Substances 0.000 description 23
- 229910052786 argon Inorganic materials 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 230000010354 integration Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 8
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- HXYXTCJDWHHCBW-UHFFFAOYSA-N acetonitrile;toluene Chemical compound CC#N.CC1=CC=CC=C1 HXYXTCJDWHHCBW-UHFFFAOYSA-N 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001476 gene delivery Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Definitions
- the invention relates to a polymer and a preparation method thereof, and belongs to the field of polymers.
- Self-assembly at the nanoscale is a key property that nature relies on to generate biological membranes.
- These membranes build a functionalized molecular framework by embedding a combination of channels, receptors, and molecular pumps in the microenvironment and functional framework. Using hydrophobic-hydrophilic interactions, these membranes self-assemble into bilayers and other structures such as vesicles.
- Self-assembled membranes are a key component if one wishes to mimic the principles of natural nanostructures.
- a range of polymer systems have been used for drug delivery, biopharmaceutical coatings, virus-assisted gene delivery, and nanoreactors through their self-assembly. These are amphiphilic diblock or triblock copolymers that self-assemble in suitable solvents into micelles, worm-like micelles, tubular structures, membranes, or vesicles.
- ABA triblock copolymers Although there are many different types of block copolymer structures, ABA triblock copolymers have received particular attention in recent years due to their inherent ability to form vesicular structures by self-assembly despite being highly hydrophobic and hydrophilic. From a biomedical perspective, polyoxazolines are particularly attractive because they provide a pseudopolypeptide architecture and were chosen as the hydrophilic block A.
- Polymethylsiloxane (PDMS) exhibits a very low glass transition temperature and is mostly liquid at room temperature due to the ionic nature of the Si- CH3 bond.
- poly(siloxanes) have very low surface energy and are extremely hydrophobic; therefore, they were chosen as the hydrophobic block B. This type of ABA triblock copolymer system has been extensively studied and has been shown to have interesting biomedical and self-assembly properties.
- the existing synthesis method constructs a series of ABA triblock backbone structure polymers through a core-first synthesis strategy, but it has the disadvantages of many synthesis steps, low yield, high polymer dispersibility, poor repeatability, and difficulty in modifying the molecular structure.
- the existing technology provides a small amount of triblock polymer preparation schemes, such as the following preparation method, which realizes the preparation of single hydroxyl-terminated triblock polymer PMOXA-PDMS-PMOXA through 4-5 steps.
- the process steps are too long, and it involves metal lithium reagents with poor stability and pyridine with high toxicity, which seriously pollutes the environment and is not conducive to industrial large-scale production.
- the technical problem to be solved by the present invention is that the existing method for synthesizing block copolymers has many synthesis steps, involves metal lithium reagents with poor stability, pyridine and other reagents with high toxicity, low yield, high polymer dispersibility, poor repeatability, and difficult molecular structure modification.
- the present invention provides a polymer and a preparation method thereof.
- the present invention provides a polymer represented by formula V:
- the R is -ORt1 , -NRt2Rt3 , -COOMe , -( CH2 ) n1SH , a 5-10 membered heteroaryl substituted by 1, 2 or 3 oxo groups, -O( CH2 ) n2OH , -OP(O)(OMe), -OP(O)(OMe)(O( CH2 ) n3N + (Et) 3 ,
- R t1 , R t2 , and R t3 are independently H, Ts, C 1 -C 6 alkyl or -(CH 2 ) n4 SH;
- n1, n3 and n4 are independently 0, 1, 2, 3, 4, 5 or 6;
- n2 is 2, 3, 4, 5, 6, 7, 8 or 9;
- the L is a
- R c is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, -CN or -NO 2 ;
- n 1, 2, 3, 4, 5 or 6;
- n 3, 4, 5, 6, 7, 8 or 9;
- Ra is ( CH2 ) n , n is 3, 4 or 5, and said Rb is hydrogen, C1 - C6 alkyl or acetyl;
- poly-2-methyloxazoline polyphospholipid, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polymethyl methacrylate, poly(N,N-dimethylacrylamide), polyacylalkylene imine, polyhydroxyalkyl acrylate, poly-2-methyloxazoline polyethylene glycol or poly-2-methyloxazoline polyphospholipid;
- the p is 20-50;
- the number of heteroatoms is independently 1, 2 or 3, and the heteroatoms are independently selected from one or more of N, O and S.
- each R 2 is independently a C 1 -C 3 alkyl group, preferably a methyl group; each m is independently any value from 1 to 22; preferably any value from 1 to 6; more preferably 1, 1.1, 1.3, 3.6, 3.8 or 5.4; further preferably 1, 1.1, 1.3 or 3.6; each w is independently any value from 1 to 22; preferably any value from 1 to 6; more preferably 3.
- the R 1 is preferably a C 1 -C 6 alkyl group, more preferably a methyl group.
- the R 1' is preferably a C 1 -C 6 alkyl group, more preferably a methyl group.
- Y is preferably a C 1 -C 6 alkyl group, more preferably a methyl group.
- the R is preferably hydroxyl, methoxy, TsO- or More preferably, hydroxyl or
- L is preferably or -CH 2 -.
- the p is preferably any value between 20 and 47, and more preferably 20 or 35.
- the R 1 is preferably methyl; the R 1' is preferably methyl;
- the R2 is preferably a methyl group; the R is preferably a hydroxyl group; the Y is preferably a methyl group; the L is preferably The m is preferably 3.6; the p is preferably 35.
- the R 1 is preferably methyl; the R 1' is preferably methyl;
- the R 2 is preferably methyl;
- the R is preferably
- the Y is preferably a methyl group;
- the L is preferably -CH 2 -;
- the m is preferably 3.6; and
- the p is preferably 35.
- the R 1 is preferably methyl; the R 1' is preferably methyl;
- the R 2 is preferably a methyl group; the R is preferably a hydroxyl group; the Y is preferably a methyl group; the L is preferably -CH 2 -; the m is preferably 1; the w is preferably 3; and the p is preferably 30.
- the R 1 is preferably methyl; the R 1' is preferably methyl;
- the R2 is preferably a methyl group; the R is preferably a hydroxyl group; the Y is preferably a methyl group; the L is preferably The m is preferably 1.1; the w is preferably 3; and the p is preferably 20.
- the R 1 is preferably methyl; the R 1' is preferably methyl;
- the R2 is preferably a methyl group; the R is preferably a hydroxyl group; the Y is preferably a methyl group; the L is preferably The m is preferably 1.3; the w is preferably 3; and the p is preferably 20.
- the polymer represented by formula V is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula V is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula V is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula V is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula V is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the present invention provides a method for preparing a polymer represented by formula V, which comprises the following steps: in a solvent and in an inert atmosphere, subjecting a polymer represented by formula Z8 and a polymer represented by formula S4 to an addition reaction as shown below under the action of a catalyst to obtain a polymer represented by formula V, that is,
- R, L, R 1 , R 1′ , Y and p are as defined above.
- the catalyst in the method for preparing the polymer represented by formula V, may be conventional in the art for such reactions, preferably H 2 PtCl 2 or a platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex solution.
- the catalyst is more preferably a platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex solution.
- the solvent in the method for preparing the polymer of formula V, may be a commonly used solvent for such reactions in the art.
- the solvent is preferably one or more of chlorinated hydrocarbon solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and nitrile solvents.
- the chlorinated hydrocarbon solvent is preferably one or more of chloroform and dichloroethane.
- the ether solvent is preferably tetrahydrofuran.
- the ester solvent is preferably ethyl acetate.
- the aromatic hydrocarbon solvent is preferably toluene.
- the nitrile solvent is preferably one or more of benzonitrile and acetonitrile.
- the solvent is preferably a mixed solvent of aromatic hydrocarbon solvents and nitrile solvents, more preferably a mixed solvent of toluene and acetonitrile.
- the volume ratio of the aromatic hydrocarbon solvent to the nitrile solvent is preferably 1:0.01-1:3; more preferably 1:1.
- the molar ratio of Z8 to S4 can be conventional in this field for such reactions, preferably 2.5-3, and more preferably 2.5.
- the molar volume ratio of Z8 to the catalyst can be conventional in this field for such reactions, preferably 15-30 mol/L.
- the platinum content in the catalyst may be conventional for such reactions in the art, preferably 1-4%, and more preferably 2%.
- the molar volume ratio of Z8 to the solvent may be conventional in the art for such reactions, preferably 0.05-0.2 mol/L, and more preferably 0.125 mol/L.
- the reaction temperature may be conventional in the art for such reactions, preferably 60 to 80°C, more preferably 60°C or 80°C.
- the reaction time of the reaction may be conventional for such reactions in the art, preferably 24 to 48 hours, more preferably 24 hours or 48 hours.
- the inert atmosphere may be conventional for such reactions in the art, preferably nitrogen atmosphere and argon atmosphere.
- the reaction may further include post-treatment.
- the post-treatment step may be conventional for such reactions in the art.
- ethanol and regenerated cellulose membranes are used for diafiltration purification.
- regenerated cellulose membranes are used for diafiltration purification.
- the molar volume ratio of the compound represented by formula Z8 to ethanol can be conventional in this field for such reactions, preferably 1:40 mol/L.
- the order of adding materials for the reaction can be conventional in the art for such reactions.
- Z8 is first dissolved in a solvent, S4 is added, and then a catalyst is added.
- the order of adding materials for the reaction is more preferably to first dissolve Z8 in a solvent, add S4 after it is completely dissolved or mostly dissolved, and then add a catalyst after it is completely dissolved.
- the specific operation of the reaction can be conventional in the art.
- a) Z8 is first dissolved in a solvent and stirred thoroughly until it is completely dissolved or mostly dissolved; b) S4 is added, and after it is dissolved, it is stirred thoroughly for 5 minutes; c) a catalyst is added and stirred thoroughly for 5-10 minutes; d) the temperature is raised and stirred.
- the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is
- the catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution;
- the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1;
- the inert atmosphere is an argon atmosphere;
- the molar ratio of Z8 to S4 is preferably 2.5;
- the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L;
- the platinum content in the catalyst is preferably 2%;
- the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L;
- the reaction temperature is 80°C; and the reaction time is 24h.
- the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is
- the catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution;
- the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1;
- the inert atmosphere is argon;
- the molar ratio of Z8 to S4 is preferably 2.5;
- the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L;
- the platinum content in the catalyst is preferably 2%;
- the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L;
- the reaction temperature is 80°C; and the reaction time is 48h.
- the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is
- the catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution;
- the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1;
- the inert atmosphere is argon;
- the molar ratio of Z8 to S4 is preferably 2.5;
- the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L;
- the platinum content in the catalyst is preferably 2%;
- the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L;
- the reaction temperature is 80°C; and the reaction time is 48h.
- the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is
- the catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution;
- the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1;
- the inert atmosphere is an argon atmosphere;
- the molar ratio of Z8 to S4 is preferably 2.5;
- the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L;
- the platinum content in the catalyst is preferably 2%;
- the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L;
- the reaction temperature is 80°C; and the reaction time is 48h.
- the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is
- the catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution;
- the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1;
- the inert atmosphere is an argon atmosphere;
- the molar ratio of Z8 to S4 is preferably 2.5;
- the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L;
- the platinum content in the catalyst is preferably 2%;
- the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L;
- the reaction temperature is 80°C; and the reaction time is 48h.
- the method for preparing the polymer of formula V also includes a method for preparing the polymer of formula Z8, which comprises the following steps: in a solvent, in an inert atmosphere, reacting the compound of formula S5, the compound of formula Z6 and the quenching agent S7 as shown below to obtain the polymer of formula Z8, that is,
- R, L and The definitions are the same as above;
- Said X is halogen, OTf or OTs
- the quenching reagent S7 is an inorganic base (such as KOH) or RH, and R is defined as above;
- the solvent in the method for preparing the polymer represented by formula Z8, may be a commonly used solvent for such reactions in the art.
- the solvent is preferably a nitrile solvent.
- the solvent is more preferably acetonitrile.
- L is preferably or -CH 2 -, and the 1 end is connected to X.
- the 2-Methyloxazoline is preferred.
- X is preferably Br, Cl or OTs.
- X is preferably Br.
- X is preferably Cl.
- X is preferably OTs.
- the quenching reagent S7 is preferably a methanol solution of potassium hydroxide
- the quenching reagent S7 is preferably a methanol solution of potassium hydroxide, more preferably a methanol solution with a potassium hydroxide concentration of 0.5M.
- the quenching reagent S7 is preferably
- the quenching reagent S7 is preferably
- the molar ratio of the compound represented by formula S5 to the compound represented by formula Z6 can be conventional in the art for such reactions, preferably 2:1-1:8, more preferably 1:1 or 1:4.
- the molar volume ratio of the compound represented by formula S5 to the quenching agent S7 can be conventional in the art for such reactions, preferably 5-20 mol/L, and more preferably 10 mol/L.
- the quenching reagent S7 when the quenching reagent S7 is When the molar ratio of the compound represented by formula S5 to the quenching agent S7 can be conventional in the art for such reactions, preferably 1:2-2:1, and more preferably 1:1.
- the quenching reagent S7 when the quenching reagent S7 is When the molar ratio of the compound represented by formula S5 to the quenching agent S7 can be conventional in the art for such reactions, preferably 1:2-2:1, and more preferably 1:1.
- the molar volume ratio of the compound represented by formula S5 to the solvent can be conventional in the art for such reactions, preferably 1:1.5 mol/L-1:3 mol/L, and more preferably 50:120 mol/L.
- the reaction temperature may be conventional for such reactions in the art, preferably 40-120°C, more preferably 80°C.
- the reaction time may be conventional for such reactions in the art, preferably 12-48 hours, and more preferably 24 hours.
- the inert atmosphere may be conventional in the art for such reactions, preferably a nitrogen atmosphere or an argon atmosphere.
- the timing of adding the quenching reagent S7 can be conventional in the art for such reactions. Preferably, it is added after the reaction is cooled to room temperature. More preferably, it is added after the reaction is cooled to room temperature and stirred for 3 hours.
- the reaction may further include post-treatment.
- the post-treatment step may be conventional for such reactions in the art.
- ethanol and regenerated cellulose membranes are used for diafiltration purification.
- regenerated cellulose membranes are used for diafiltration purification.
- the molar volume ratio of the compound represented by formula S5 to ethanol can be conventional in the art for such reactions, preferably 5:70 mol/L.
- the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is a methanol solution with a potassium hydroxide concentration of 0.5M; the polymer represented by the formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and the compound represented by formula Z6
- the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:4; the molar volume ratio of the compound represented by formula S5 to the quenching reagent S7 is 10 mol/L; the molar volume ratio of the compound represented by formula S5 to the solvent is 50:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
- the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is The polymer represented by formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and the compound represented by formula Z6
- the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:4; the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:1; the molar volume ratio of the compound represented by formula S5 to the solvent is 50:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
- the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is The polymer represented by formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and the compound represented by formula Z6
- the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:4; the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:1; the molar volume ratio of the compound represented by formula S5 to the solvent is 50:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
- the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is The polymer represented by formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and the compound represented by formula Z6 The molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:1; the molar volume ratio of the compound represented by formula S5 to the solvent is 50:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
- the solvent is acetonitrile;
- the compound represented by S5 is The quenching reagent S7 is a methanol solution with a potassium hydroxide concentration of 0.5M;
- the polymer represented by the formula Z8 is The compound represented by Z6 is 2-methyloxazoline;
- the compound represented by formula S5 and formula Z6 The molar ratio of the compounds shown is 1:1; the molar volume ratio of the compound shown in formula S5 and the quenching reagent S7 is 2.5 mol/L; the molar volume ratio of the compound shown in formula S5 and the solvent is 12.5:120 mol/L;
- the reaction is carried out at a reaction temperature of 80°C;
- the reaction time is 24 hours;
- the inert atmosphere is argon;
- the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
- the present invention provides a polymer represented by formula Z8:
- R, L and The definitions are the same as above.
- the polymer represented by formula Z8 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula Z8 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula Z8 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula Z8 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula Z8 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula Z8 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the polymer represented by formula Z8 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the present invention provides a method for preparing a polymer represented by formula Z8, which comprises the following steps: in a solvent and in an inert atmosphere, reacting a compound represented by formula S5, a compound represented by formula Z6 and a quenching agent S7 as shown below to obtain a polymer represented by formula Z8, that is,
- R, X, quenching reagent S7, L and The definitions and reaction conditions such as reaction temperature, reaction time, molar ratio of each reactant, reaction operation and the like are the same as described above.
- a "-" at the end of a group means that the group is attached to the rest of the molecule through that site.
- -CN refers to a cyano group.
- alkyl refers to a linear or branched, saturated, monovalent hydrocarbon group having a specified number of carbon atoms.
- C1 - C6 alkyl includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, etc.
- alkoxy refers to the group R X -O-, where R X is defined as the term “alkyl”. Alkoxy includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, and the like.
- alkylthio refers to the group R X -S-, where R X is defined as the term "alkyl”.
- Alkylthio includes, but is not limited to, methylthio, ethylthio, n-propylthio, isopropylthio, and the like.
- aryl refers to a cyclic, unsaturated, monovalent hydrocarbon group with a specified number of carbon atoms (e.g., C 6 -C 10 ), which is a single ring or multiple rings (e.g., 2 or 3). When it is a multiple ring, the single rings share two atoms and a bond, and at least one ring is aromatic.
- the aryl group is connected to the rest of the molecule through an aromatic ring or a non-aromatic ring.
- Aryl groups include, but are not limited to, phenyl, naphthyl, wait.
- heteroaryl refers to a cyclic, unsaturated, monovalent group having a specified number of ring atoms (e.g., 5-10 members), a specified number of heteroatoms (e.g., 1, 2, or 3), a specified type of heteroatom (one or more of N, O, and S), which is a single ring or multiple rings, with two atoms and a bond shared between the single rings, and at least one ring being aromatic.
- a heteroaryl group is attached to the rest of the molecule through a carbon atom or a heteroatom; a heteroaryl group is attached to the rest of the molecule through a ring with heteroatoms or a ring without heteroatoms; a heteroaryl group is attached to the rest of the molecule through a ring with aromatic properties or a ring without aromatic properties.
- Heteroaryl groups include, but are not limited to: wait.
- the reagents and raw materials used in the present invention are commercially available.
- the positive progress of the present invention is that the polymer of the present invention can self-assemble into a vesicle structure in a solution, and the vesicle has good stability.
- the preparation method of the present invention has the advantages of fewer synthesis steps, mild reaction conditions, high yield, low polymer dispersibility, good repeatability, and accurate molecular weight control and diversified modification of the end-capping group and the connecting group between the hydrophobic block and the hydrophilic block of the polymer.
- the synthetic route of triblock polymer P1 is as follows:
- Step 1 synthesis of prepolymer S4-1: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 1.5 mL of 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 8.49 mmol) with a syringe.
- the molar ratio of S1 to S2 is 8:1.
- S1 can be slightly excessive, and argon gas is used for deoxygenation three times.
- Step 2 synthesis of prepolymer Z8-1: dry vinyl compound S5-1 (7.6 g, 152.62 g/mol, 50 mmol) and reaction raw material Z6-1 (17 g, 85.1 g/mol, 200 mmol) were mixed and dissolved in dry acetonitrile (120 mL) in argon. React at 80 ° C for 24 h. The reaction was completed by nuclear magnetic hydrogen spectrum. After the reaction was complete, the mixture was cooled to room temperature, and then 5 ml of 0.5 M methanol solution containing potassium hydroxide S7-1 (0.48 g) was added to the mixture to terminate the reaction, and stirred for 3 hours.
- Step 3 synthesis of triblock P1: In argon, the reaction raw material S4-1 (3.2 g, 3200 g/mol, 1 mmol) and the dry reaction raw material Z8-1 (1.1 g, 440 g/mol, 2.5 mmol) were dissolved in 20 ml of dry toluene acetonitrile mixed solvent (1/1). After sufficient dissolution, 120 uL Karstedt Catalyst (in xylene, Pt ⁇ 2%) was added, and then the temperature was raised to 80°C and stirred at 80°C for 24 h. After the reaction was complete, the mixture was cooled to room temperature and filtered.
- the synthetic route of triblock polymer P2 is as follows:
- Step 1 synthesis of prepolymer S4-1: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 1.5 mL of 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 8.49 mmol) with a syringe.
- the molar ratio of S1 to S2 is 8:1.
- S1 can be slightly excessive and deoxygenated three times.
- Step 2 synthesis of prepolymer Z8-2: dry vinyl compound S5-2 (50mmol) (6.1g, 120.99g/mol, 50mmol) and reaction raw material Z6-1 (17g, 85.1g/mol, 200mmol) were mixed and dissolved in dry acetonitrile (120mL) in argon. React at 80°C for 24h. The reaction was completed by H NMR. After the reaction was complete, the mixture was cooled to room temperature, and then the reaction was terminated by adding S7-2 (14.7g, 147.1g/mol, 50mmol) and stirred for 3 hours. After removing the solvent under reduced pressure, the product was dissolved in 100ml of deionized water and the residual S7-2 was removed by filtration.
- Step 3 synthesis of triblock P2: In argon, the reaction raw material S4-1 (3.2 g, 3200 g/mol, 1 mmol) and the dry reaction raw material Z8-2 (1.2 g, 493 g/mol, 2.5 mmol) were dissolved in 20 ml of dry toluene/acetonitrile mixed solvent (1/1). After the raw materials were fully dissolved at room temperature, 120 uL Karstedt catalyst (in xylene, Pt ⁇ 2%) was added, the temperature was raised to 80°C, and stirred at 80°C for 48 h. After the reaction was complete, the mixture was cooled to room temperature and filtered.
- the reaction raw material S4-1 3.2 g, 3200 g/mol, 1 mmol
- the dry reaction raw material Z8-2 1.2 g, 493 g/mol, 2.5 mmol
- the synthetic route of the pentablock polymer P3 is as follows:
- Step 1 synthesis of prepolymer S4-2: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 1.7 mL 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 9.67 mmol) with a syringe.
- the molar ratio of S1 to S2 is 7:1.
- S1 can be slightly excessive, and argon gas is used for deoxygenation three times.
- Step 2 Synthesis of prepolymer Z8-3: Mix the dried vinyl compound S5-2 (6.1 g, 120.99 g/mol, 50 mmol) and the reaction raw material Z6-1 (17 g, 85.1 g/mol, 200 mmol) in dry acetonitrile (120 mL) in argon. React at 80°C for 24 h. The nuclear magnetic hydrogen spectrum confirms that the reaction is complete. After the reaction is complete, the mixture is cooled to room temperature, and then the reaction is terminated by adding S7-3 (7.5 g, 150.2 g/mol, 50 mmol) and stirred for 3 hours.
- S7-3 7.5 g, 150.2 g/mol, 50 mmol
- Step 3 synthesis of triblock P3: In argon, the reaction raw material S4-2 (2.3 g, 2354 g/mol, 1 mmol) and the dry reaction raw material Z8-3 (0.7 g, 289 g/mol, 2.5 mmol)) were dissolved in 20 ml of dry toluene/acetonitrile mixed solvent (1/1). After the raw materials were fully dissolved at room temperature, 120 uL of Karstedt catalyst (in xylene, Pt ⁇ 2%) was added, the temperature was raised to 80°C, and stirred at 80°C for 48 h. After the reaction was complete, the mixture was cooled to room temperature and filtered.
- Karstedt catalyst in xylene, Pt ⁇ 2%
- the synthetic route of the pentablock polymer P4 is as follows:
- Step 1 synthesis of prepolymer S4-3: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 2.4 mL 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 13.54 mmol) with a syringe.
- the molar ratio of S1 to S2 is 5:1.
- S1 can be slightly excessive, and argon gas is used for deoxygenation three times.
- Step 2 synthesis of prepolymer Z8-4: dry vinyl compound S5-1 (7.6g, 152.62g/mol, 50mmol) and reaction raw material Z6-1 (4.3g, 85.1g/mol, 50mmol) were mixed and dissolved in dry acetonitrile (120mL) in argon. React at 80°C for 24h. The reaction was completed by H NMR spectrum. After the reaction was complete, the mixture was cooled to room temperature, and then the reaction was terminated by adding S7-3 (7.5g, 150.2g/mol, 50mmol) and stirred for 3 hours. After the solvent was removed under reduced pressure, the product was dissolved in 100ml of dichloromethane, and the residual inorganic salts and excess potassium hydroxide were filtered out. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain vinyl-terminated PMOXA prepolymer Z8-4 (16.1g, yield 88%). Its structure and degree of polymerization were determined by H NMR spectrum integration.
- Step 3 synthesis of triblock P4: In argon, the reaction raw material S4-3 (1.6 g, 1628 g/mol, 1 mmol) and the dry reaction raw material Z8-4 (0.92 g, 366 g/mol, 2.5 mmol) were dissolved in 20 ml of dry toluene/acetonitrile mixed solvent (1/1). After the raw materials were fully dissolved at room temperature, 120 uL of Karstedt catalyst (in xylene, Pt ⁇ 2%) was added, the temperature was raised to 80°C, and stirred at 80°C for 48 h. After the reaction was complete, the mixture was cooled to room temperature and filtered.
- Karstedt catalyst in xylene, Pt ⁇ 2%
- the synthetic route of the pentablock polymer P5 is as follows:
- Step 1 synthesis of prepolymer S4-3: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 2.4 mL 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 13.54 mmol) with a syringe.
- the molar ratio of S1 to S2 is 5:1.
- S1 can be slightly excessive, and argon gas is used for deoxygenation three times.
- Step 2 Synthesis of prepolymer Z8-9-1: In a nitrogen atmosphere, the dried vinyl compound S5-1 (7.6 g, 152.62 g/mol, 50 mmol)) and the reaction raw material S7-3 (15.0 g, 150.2 g/mol, 100 mmol) were mixed and dissolved in dry 1,4-dioxane (120 mL). Solid potassium hydroxide (5.6 g, 56.10 g/mol, 100 mmol) was added and reacted at 50°C for 48 h. The nuclear magnetic hydrogen spectrum confirmed that the reaction was complete.
- Step 3 Synthesis of prepolymer Z8-5-3: In a nitrogen atmosphere, the dried vinyl compound Z8-9-1 (7.9 g, 270 g/mol, 29.2 mmol)) and the reaction raw material S11 triethylamine (3.5 g, 101.2 g/mol, 35.0 mmol) were mixed and dissolved in dry dichloromethane (120 mL), and cooled and stirred in an ice bath for 15 minutes. The reaction raw material S10 p-toluenesulfonyl chloride (5.4 g, 154.6 g/mol, 35.0 mmol) was added in 3 portions. The temperature was restored to 25 ° C and stirred for 24 hours.
- Step 4 synthesis of prepolymer Z8-5: dry vinyl compound Z8-5-3 (5.3 g, 420.5 g/mol, 12.5 mmol) and reaction raw material Z6-1 (1.1 g, 85.1 g/mol, 12.5 mmol) were mixed and dissolved in dry acetonitrile (120 mL) in argon. React at 80 ° C for 24 h. The reaction was completed by nuclear magnetic hydrogen spectrum. After the reaction was complete, the mixture was cooled to room temperature, and then 5 ml of 0.5 M methanol solution containing potassium hydroxide S7-1 (0.48 g) was added to the mixture to terminate the reaction, and stirred for 3 hours.
- Step 5 synthesis of triblock P5:
- the reaction raw material S4-3 (1.6 g, 1628 g/mol, 1 mmol) and the dry reaction raw material Z8-5 (0.96 g, 385 g/mol, 2.5 mmol) were dissolved in 20 ml of dry toluene/acetonitrile mixed solvent (1/1).
- 120 uL of Karstedt catalyst (in xylene, Pt ⁇ 2%) was added, the temperature was raised to 80°C, and stirred at 80°C for 48 h. After the reaction was complete, the mixture was cooled to room temperature and filtered.
- the droplets of the polymer P5 of the present application can exist stably for more than 30 minutes, have good uniformity, and there is no obvious fusion between the droplets.
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a polymer and a preparation method therefor. Disclosed in the present invention is a polymer represented by formula V, which polymer has good droplet stability. Further disclosed in the present invention is a method for preparing the polymer represented by formula V, which method comprises the following steps: in a solvent, subjecting a polymer represented by formula Z8 and a polymer represented by formula S4 to an addition reaction as shown below in an inert atmosphere under the action of a catalyst to obtain a polymer represented by formula V. When the polymer represented by formula V is prepared by using the method, there are few synthesis steps, the reaction conditions are mild, the yield is high, the polymer dispersity is low, the repeatability is good, and accurate molecular weight control and end-capping groups are achieved.
Description
本发明涉及一种聚合物及其制备方法,属于聚合物领域。The invention relates to a polymer and a preparation method thereof, and belongs to the field of polymers.
纳米尺度上的自组装是自然界产生生物膜所依赖的关键性质。这些膜通过在微环境和功能框架中嵌入通道、受体和分子泵的结合,构建了一个功能化的分子框架。利用疏水-亲水相互作用,这些膜自组装成双层和囊泡等其他结构。如果希望模仿自然纳米结构的原理,自组装膜是一个关键的组成部分。近年来,一系列聚合物体系通过其自组装,被用于药物递送,生物药物涂层,病毒辅助基因传递,以及纳米反应器。这些是两亲性二嵌段或三嵌段共聚物在适宜的溶剂中自组装成胶束,蠕虫状胶束,管状的结构、膜或囊泡。Self-assembly at the nanoscale is a key property that nature relies on to generate biological membranes. These membranes build a functionalized molecular framework by embedding a combination of channels, receptors, and molecular pumps in the microenvironment and functional framework. Using hydrophobic-hydrophilic interactions, these membranes self-assemble into bilayers and other structures such as vesicles. Self-assembled membranes are a key component if one wishes to mimic the principles of natural nanostructures. In recent years, a range of polymer systems have been used for drug delivery, biopharmaceutical coatings, virus-assisted gene delivery, and nanoreactors through their self-assembly. These are amphiphilic diblock or triblock copolymers that self-assemble in suitable solvents into micelles, worm-like micelles, tubular structures, membranes, or vesicles.
虽然嵌段共聚物的结构有很多种,ABA三嵌段共聚物近些年来得到了特别的关注,因为其具有通过自组装形成囊泡结构的固有能力,尽管具有高度的疏水性和亲水性。从生物医学的角度来看,聚恶唑啉能提供了假聚多肽体系结构,因此尤其具有吸引力,被选为亲水性嵌段A。而聚甲基硅氧烷(PDMS),由于Si-CH
3键所具有的离子属性,则表现出很低的玻璃化转变温度,在室温下多呈现液体状态。此外,聚(硅氧烷)具有非常低的表面能和极高的疏水性;因此,他们被选为疏水性嵌段B。对这类ABA三嵌段共聚物体系的研究,得到了大量得研究,并被证明具有有趣的生物医学和自组装特性。
Although there are many different types of block copolymer structures, ABA triblock copolymers have received particular attention in recent years due to their inherent ability to form vesicular structures by self-assembly despite being highly hydrophobic and hydrophilic. From a biomedical perspective, polyoxazolines are particularly attractive because they provide a pseudopolypeptide architecture and were chosen as the hydrophilic block A. Polymethylsiloxane (PDMS), on the other hand, exhibits a very low glass transition temperature and is mostly liquid at room temperature due to the ionic nature of the Si- CH3 bond. In addition, poly(siloxanes) have very low surface energy and are extremely hydrophobic; therefore, they were chosen as the hydrophobic block B. This type of ABA triblock copolymer system has been extensively studied and has been shown to have interesting biomedical and self-assembly properties.
现有的合成方法,通过以核心优先的合成策略,构建了一系列ABA三嵌段骨架结构聚合物,但却具有合成步骤多,收率低,聚合物分散性高,重复性差,且分子结构较难修饰等缺点。The existing synthesis method constructs a series of ABA triblock backbone structure polymers through a core-first synthesis strategy, but it has the disadvantages of many synthesis steps, low yield, high polymer dispersibility, poor repeatability, and difficulty in modifying the molecular structure.
现有的技术提供了少量三嵌段聚合物的制备方案,例如下述制备方法,经过4-5步,分别实现了对单一羟基封端三嵌段聚合物PMOXA-PDMS-PMOXA的制备。工艺中步骤过长,且涉及稳定性不佳的金属锂试剂,毒性较高的吡啶等试剂,环境污染严重,不利于工业大剂量生产。The existing technology provides a small amount of triblock polymer preparation schemes, such as the following preparation method, which realizes the preparation of single hydroxyl-terminated triblock polymer PMOXA-PDMS-PMOXA through 4-5 steps. The process steps are too long, and it involves metal lithium reagents with poor stability and pyridine with high toxicity, which seriously pollutes the environment and is not conducive to industrial large-scale production.
发明内容Summary of the invention
本发明要解决的技术问题是现有合成嵌段共聚物的方法合成步骤多,涉及稳定性不佳的金属锂试剂,毒性较高的吡啶等试剂,收率低,聚合物分散性高,重复性差,且分子结构较难修饰等缺点。为此,本发明提供了一种聚合物及其制备方法。The technical problem to be solved by the present invention is that the existing method for synthesizing block copolymers has many synthesis steps, involves metal lithium reagents with poor stability, pyridine and other reagents with high toxicity, low yield, high polymer dispersibility, poor repeatability, and difficult molecular structure modification. To this end, the present invention provides a polymer and a preparation method thereof.
本发明提供了一种式V所示聚合物:The present invention provides a polymer represented by formula V:
其中,in,
所述R为-OR
t1、-NR
t2R
t3、-COOMe、-(CH
2)
n1SH、被1、2或3个氧代基取代的5-10元杂芳基、-O(CH
2)
n2OH、-OP(O)(OMe)、-OP(O)(OMe)(O(CH
2)
n3N
+(Et)
3,
The R is -ORt1 , -NRt2Rt3 , -COOMe , -( CH2 ) n1SH , a 5-10 membered heteroaryl substituted by 1, 2 or 3 oxo groups, -O( CH2 ) n2OH , -OP(O)(OMe), -OP(O)(OMe)(O( CH2 ) n3N + (Et) 3 ,
其中,所述R
t1、R
t2、R
t3独立地为H、Ts、C
1-C
6烷基或-(CH
2)
n4SH;
Wherein, R t1 , R t2 , and R t3 are independently H, Ts, C 1 -C 6 alkyl or -(CH 2 ) n4 SH;
n1、n3和n4独立地为0、1、2、3、4、5或6;n1, n3 and n4 are independently 0, 1, 2, 3, 4, 5 or 6;
n2为2、3、4、5、6、7、8或9;n2 is 2, 3, 4, 5, 6, 7, 8 or 9;
所述
中,所述R
c为氢、C
1-C
6烷基、C
1-C
6烷氧基、-CN或-NO
2;
Said wherein R c is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, -CN or -NO 2 ;
所述
中,所述R
a为(CH
2)
n,n为3、4或5,所述R
b为氢、C
1-C
6烷基或乙酰基;
Said wherein said Ra is ( CH2 ) n , n is 3, 4 or 5, and said Rb is hydrogen, C1 - C6 alkyl or acetyl;
所述
为聚2-甲基恶唑啉、聚磷脂、聚乙二醇、聚乙烯醇、聚乙烯吡咯烷酮、聚丙烯酰胺、聚甲基丙烯酸甲酯、聚(N,N-二甲基丙烯酰胺)、聚酰基亚烷基亚胺、聚羟基烷基丙烯酸酯、聚2-甲基恶唑啉聚乙二醇或聚2-甲基恶唑啉聚磷脂;
Said It is poly-2-methyloxazoline, polyphospholipid, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polymethyl methacrylate, poly(N,N-dimethylacrylamide), polyacylalkylene imine, polyhydroxyalkyl acrylate, poly-2-methyloxazoline polyethylene glycol or poly-2-methyloxazoline polyphospholipid;
所述R
1为C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
6-C
12芳基、-(CH
2)
nOH、
或-(CH
2)
n-CH=CH
2,其中,n为3、4或5;
The R 1 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 12 aryl, -(CH 2 ) n OH, or -(CH 2 ) n -CH=CH 2 , wherein n is 3, 4 or 5;
所述R
1’为C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
6-C
12芳基、-(CH
2)
nOH、
或-(CH
2)
n-CH=CH
2,其中,n为3、4或5;
The R 1' is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 12 aryl, -(CH 2 ) n OH, or -(CH 2 ) n -CH=CH 2 , wherein n is 3, 4 or 5;
所述Y为C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
6-C
12芳基、-(CH
2)
nOH、
或-(CH
2)
n-CH=CH
2,其中,n为3、4或5;
The Y is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 12 aryl, -(CH 2 ) n OH, or -(CH 2 ) n -CH=CH 2 , wherein n is 3, 4 or 5;
所述p为20-50;The p is 20-50;
所述的5-10元杂芳基中,杂原子的数量独立地为1个、2个或3个,所述杂原子独立地选自N、O和S中的一种或多种。In the 5-10 membered heteroaryl group, the number of heteroatoms is independently 1, 2 or 3, and the heteroatoms are independently selected from one or more of N, O and S.
在一些实施方案中,所述
优选为
其中,每个R
2各自独立地为C
1-C
3烷基,优选为甲基;每个m各自独立地为1-22的任意数值;优选为1-6的任意数值;更优选1、1.1、1.3、3.6、3.8或5.4;进一步优选1、1.1、1.3或3.6;每个w各自独立地为1-22的任意数值;优选为1-6的任意数值;更优选为3。
In some embodiments, the Preferably Wherein, each R 2 is independently a C 1 -C 3 alkyl group, preferably a methyl group; each m is independently any value from 1 to 22; preferably any value from 1 to 6; more preferably 1, 1.1, 1.3, 3.6, 3.8 or 5.4; further preferably 1, 1.1, 1.3 or 3.6; each w is independently any value from 1 to 22; preferably any value from 1 to 6; more preferably 3.
在一些实施方案中,所述R
1优选为C
1-C
6烷基。更优选为甲基。
In some embodiments, the R 1 is preferably a C 1 -C 6 alkyl group, more preferably a methyl group.
在一些实施方案中,所述R
1’优选为C
1-C
6烷基。更优选为甲基。
In some embodiments, the R 1' is preferably a C 1 -C 6 alkyl group, more preferably a methyl group.
在一些实施方案中,所述Y优选为C
1-C
6烷基。更优选为甲基。
In some embodiments, Y is preferably a C 1 -C 6 alkyl group, more preferably a methyl group.
在一些实施方案中,所述R优选为羟基、甲氧基、TsO-或
更优选羟基或
In some embodiments, the R is preferably hydroxyl, methoxy, TsO- or More preferably, hydroxyl or
在一些实施方案中,所述p优选为20-47的任意数值。更优选为20或35。In some embodiments, the p is preferably any value between 20 and 47, and more preferably 20 or 35.
在一些实施方案中,所述R
1优选为甲基;所述R
1’优选为甲基;所述
优选为
所述R
2优选为甲基;所述R优选为羟基;所述Y优选为甲基;所述L优选为
所述m优选为3.6;所述p优选为35。
In some embodiments, the R 1 is preferably methyl; the R 1' is preferably methyl; Preferably The R2 is preferably a methyl group; the R is preferably a hydroxyl group; the Y is preferably a methyl group; the L is preferably The m is preferably 3.6; the p is preferably 35.
在一些实施方案中,所述R
1优选为甲基;所述R
1’优选为甲基;所述
优选为
所述R
2优选为甲基;所述R优选为
所述Y优选为甲基;所述L优选为-CH
2-;所述m优选为3.6;所述p优选为35。
In some embodiments, the R 1 is preferably methyl; the R 1' is preferably methyl; Preferably The R 2 is preferably methyl; the R is preferably The Y is preferably a methyl group; the L is preferably -CH 2 -; the m is preferably 3.6; and the p is preferably 35.
在一些实施方案中,所述R
1优选为甲基;所述R
1’优选为甲基;所述
优选为
所述R
2优选为甲基;所述R优选为羟基;所述Y优选为甲基;所述L优选为-CH
2-;所述m优选为1;所述w优选为3;所述p优选为30。
In some embodiments, the R 1 is preferably methyl; the R 1' is preferably methyl; Preferably The R 2 is preferably a methyl group; the R is preferably a hydroxyl group; the Y is preferably a methyl group; the L is preferably -CH 2 -; the m is preferably 1; the w is preferably 3; and the p is preferably 30.
在一些实施方案中,所述R
1优选为甲基;所述R
1’优选为甲基;所述
优选为
所述R
2优选为甲基;所述R优选为羟基;所述Y优选为甲基;所述L优选为
所述m优选为1.1;所述w优选为3;所述p优选为20。
In some embodiments, the R 1 is preferably methyl; the R 1' is preferably methyl; Preferably The R2 is preferably a methyl group; the R is preferably a hydroxyl group; the Y is preferably a methyl group; the L is preferably The m is preferably 1.1; the w is preferably 3; and the p is preferably 20.
在一些实施方案中,所述R
1优选为甲基;所述R
1’优选为甲基;所述
优选为
所述R
2优选为甲基;所述R优选为羟基;所述Y优选为甲基;所述L优选为
所述m优选为1.3;所述w优选为3;所述p优选为20。
In some embodiments, the R 1 is preferably methyl; the R 1' is preferably methyl; Preferably The R2 is preferably a methyl group; the R is preferably a hydroxyl group; the Y is preferably a methyl group; the L is preferably The m is preferably 1.3; the w is preferably 3; and the p is preferably 20.
本发明提供了一种式V所示聚合物的制备方法,其包括如下步骤:在溶剂中,在惰性气氛中,将式Z8所示聚合物和式S4所示聚合物在催化剂的作用下进行如下所示的加成反应,制得式V所示聚合物,即可,The present invention provides a method for preparing a polymer represented by formula V, which comprises the following steps: in a solvent and in an inert atmosphere, subjecting a polymer represented by formula Z8 and a polymer represented by formula S4 to an addition reaction as shown below under the action of a catalyst to obtain a polymer represented by formula V, that is,
其中,in,
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述催化剂可为本领域此类反应常规。优选为H
2PtCl
2或铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液。所述催化剂更优选为铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液。
In some embodiments, in the method for preparing the polymer represented by formula V, the catalyst may be conventional in the art for such reactions, preferably H 2 PtCl 2 or a platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex solution. The catalyst is more preferably a platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex solution.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述溶剂可为本领域此类反应常用溶剂。所述溶剂优选氯代烃类溶剂、醚类溶剂、酯类溶剂、芳烃类溶剂和腈类溶剂中的一种或多种。所述的氯代烃类溶剂优选氯仿和二氯乙烷一种或多种。所述的醚类溶剂优选四氢呋喃。所述的酯类溶剂优选乙酸乙酯。所述的芳烃类溶剂优选甲苯。所述的腈类溶剂优选苯甲腈和乙腈的一种或多种。所述溶剂优选芳烃类溶剂和腈类溶剂的混合溶剂,更优选甲苯和乙腈混合溶剂。在所述芳烃类溶剂和腈类溶剂的混合溶剂中,所述芳烃类溶剂和腈类溶剂的体积比优选为1:0.01-1:3;更优选1:1。In some embodiments, in the method for preparing the polymer of formula V, the solvent may be a commonly used solvent for such reactions in the art. The solvent is preferably one or more of chlorinated hydrocarbon solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and nitrile solvents. The chlorinated hydrocarbon solvent is preferably one or more of chloroform and dichloroethane. The ether solvent is preferably tetrahydrofuran. The ester solvent is preferably ethyl acetate. The aromatic hydrocarbon solvent is preferably toluene. The nitrile solvent is preferably one or more of benzonitrile and acetonitrile. The solvent is preferably a mixed solvent of aromatic hydrocarbon solvents and nitrile solvents, more preferably a mixed solvent of toluene and acetonitrile. In the mixed solvent of aromatic hydrocarbon solvents and nitrile solvents, the volume ratio of the aromatic hydrocarbon solvent to the nitrile solvent is preferably 1:0.01-1:3; more preferably 1:1.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述Z8与S4的摩尔比可为本领域此类反应常规。优选2.5-3。更优选2.5。In some embodiments, in the method for preparing the polymer represented by formula V, the molar ratio of Z8 to S4 can be conventional in this field for such reactions, preferably 2.5-3, and more preferably 2.5.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述Z8与所述催化剂的摩尔体积比可为本领域此类反应常规。优选15-30mol/L。In some embodiments, in the method for preparing the polymer represented by formula V, the molar volume ratio of Z8 to the catalyst can be conventional in this field for such reactions, preferably 15-30 mol/L.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述催化剂中铂含量可为本领域此类反应常规。优选为1-4%。更优选2%。In some embodiments, in the method for preparing the polymer represented by formula V, the platinum content in the catalyst may be conventional for such reactions in the art, preferably 1-4%, and more preferably 2%.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述Z8与所述溶剂的摩尔体积比可为本领域此类反应常规。优选0.05-0.2mol/L。更优选为0.125mol/L。In some embodiments, in the method for preparing the polymer represented by formula V, the molar volume ratio of Z8 to the solvent may be conventional in the art for such reactions, preferably 0.05-0.2 mol/L, and more preferably 0.125 mol/L.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述反应的温度可为本领域此类反应常规。优选60~80℃。更优选60℃或80℃。In some embodiments, in the method for preparing the polymer represented by formula V, the reaction temperature may be conventional in the art for such reactions, preferably 60 to 80°C, more preferably 60°C or 80°C.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述反应的反应时间可为本领域此类反应常规。优选24~48h。更优选24h或48h。In some embodiments, in the method for preparing the polymer represented by formula V, the reaction time of the reaction may be conventional for such reactions in the art, preferably 24 to 48 hours, more preferably 24 hours or 48 hours.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述惰性气氛可为本领域此类反应常规。优选氮气气氛和氩气气氛。In some embodiments, in the method for preparing the polymer represented by Formula V, the inert atmosphere may be conventional for such reactions in the art, preferably nitrogen atmosphere and argon atmosphere.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述反应还可包括后处理。所述的后处理步骤可为本领域此类反应常规。优选使用乙醇和再生纤维素膜进行渗滤纯化。更优选使用再生纤维素膜(Millipore,截留分子量为1K)进行渗滤纯化。In some embodiments, in the preparation method of the polymer shown in Formula V, the reaction may further include post-treatment. The post-treatment step may be conventional for such reactions in the art. Preferably, ethanol and regenerated cellulose membranes are used for diafiltration purification. More preferably, regenerated cellulose membranes (Millipore, molecular weight cut-off is 1K) are used for diafiltration purification.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述后处理中,所述式Z8所示化合物与乙醇的摩尔体积比可为本领域此类反应常规。优选为1:40mol/L。In some embodiments, in the method for preparing the polymer represented by formula V, in the post-treatment, the molar volume ratio of the compound represented by formula Z8 to ethanol can be conventional in this field for such reactions, preferably 1:40 mol/L.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述反应的加料顺序可为本领域此类 反应常规。优选先将Z8溶于溶剂,后加入S4,再加入催化剂。所述反应的加料顺序更优选先将Z8溶于溶剂,待其完全溶解或大部分溶解后,加入S4,待其完全溶解后,再加入催化剂。In some embodiments, in the preparation method of the polymer shown in formula V, the order of adding materials for the reaction can be conventional in the art for such reactions. Preferably, Z8 is first dissolved in a solvent, S4 is added, and then a catalyst is added. The order of adding materials for the reaction is more preferably to first dissolve Z8 in a solvent, add S4 after it is completely dissolved or mostly dissolved, and then add a catalyst after it is completely dissolved.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述反应具体操作可为本领域此类反应常规。优选a)先将Z8溶于溶剂,充分搅拌至完全溶解或大部分溶解;b)加入S4,待其溶解,充分搅拌5分钟;c)加入催化剂,充分搅拌5-10分钟;d)升温搅拌。In some embodiments, in the method for preparing the polymer represented by formula V, the specific operation of the reaction can be conventional in the art. Preferably, a) Z8 is first dissolved in a solvent and stirred thoroughly until it is completely dissolved or mostly dissolved; b) S4 is added, and after it is dissolved, it is stirred thoroughly for 5 minutes; c) a catalyst is added and stirred thoroughly for 5-10 minutes; d) the temperature is raised and stirred.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述式Z8所示聚合物为
所述式S4所示聚合物为
所述式V所示聚合物为
所述催化剂为铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液;所述溶剂为甲苯和乙腈混合溶剂;所述甲苯和乙腈的体积比为1:1;所述惰性气氛为氩气气氛;所述Z8与S4的摩尔比优选2.5;所述Z8与所述催化剂的摩尔体积比优选125:6mol/L;所述催化剂中铂含量优选为2%;所述Z8与所述溶剂的摩尔体积比优选0.125mol/L;所述反应的温度为80℃;所述反应的反应时间为24h。
In some embodiments, in the method for preparing the polymer represented by formula V, the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is The catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution; the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1; the inert atmosphere is an argon atmosphere; the molar ratio of Z8 to S4 is preferably 2.5; the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L; the platinum content in the catalyst is preferably 2%; the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L; the reaction temperature is 80°C; and the reaction time is 24h.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述式Z8所示聚合物为
所述式S4所示聚合物为
所述式V所示聚合物为
所述催化剂为铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液;所述溶剂为甲苯和乙腈混合溶剂;所述甲苯和乙腈的体积比为1:1;所述惰性气氛为氩气;所述Z8与S4的摩尔比优选2.5;所述Z8与所述催化剂的摩尔体积比优选125:6mol/L;所述催化剂中铂含量优选为2%;所述Z8与所述溶剂的摩尔体积比优选0.125mol/L;所述反应的温度为80℃;所述反应的反应时间为48h。
In some embodiments, in the method for preparing the polymer represented by formula V, the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is The catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution; the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1; the inert atmosphere is argon; the molar ratio of Z8 to S4 is preferably 2.5; the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L; the platinum content in the catalyst is preferably 2%; the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L; the reaction temperature is 80°C; and the reaction time is 48h.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述式Z8所示聚合物为
所述式S4所示聚合物为
所述式V所示聚合物为
所述催化剂为铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液;所述溶剂为甲苯和乙腈混合溶剂;所述甲苯和乙腈的体积比为1:1;所述惰性气氛为氩气;所述Z8与S4的摩尔比优选2.5;所述Z8与所述催化剂的摩尔体积比优选125:6mol/L;所述催化剂中铂含量优选为2%;所述Z8与所述溶剂的摩尔体积比优选0.125mol/L;所述反应的温度为80℃;所述反应的反应时间为48h。
In some embodiments, in the method for preparing the polymer represented by formula V, the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is The catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution; the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1; the inert atmosphere is argon; the molar ratio of Z8 to S4 is preferably 2.5; the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L; the platinum content in the catalyst is preferably 2%; the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L; the reaction temperature is 80°C; and the reaction time is 48h.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述式Z8所示聚合物为
所述式S4所示聚合物为
所述式V所示聚合物为
所述催化剂为铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液;所述溶剂为甲苯和乙腈混合溶剂;所述甲苯和乙腈的体积比为1:1;所述惰性气氛为氩气气氛;所述Z8与S4的摩尔比优选2.5;所述Z8与所述催化剂的摩尔体积比优选125:6mol/L;所述催化剂中铂含量优选为2%;所述Z8与所述溶剂的摩尔体积比优选0.125mol/L;所述反应的温度为80℃;所述反应的反应时间为48h。
In some embodiments, in the method for preparing the polymer represented by formula V, the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is The catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution; the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1; the inert atmosphere is an argon atmosphere; the molar ratio of Z8 to S4 is preferably 2.5; the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L; the platinum content in the catalyst is preferably 2%; the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L; the reaction temperature is 80°C; and the reaction time is 48h.
在一些实施方案中,在所述式V所示聚合物的制备方法中,所述式Z8所示聚合物为
所述式S4所示聚合物为
所述式V 所示聚合物为
所述催化剂为铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液;所述溶剂为甲苯和乙腈混合溶剂;所述甲苯和乙腈的体积比为1:1;所述惰性气氛为氩气气氛;所述Z8与S4的摩尔比优选2.5;所述Z8与所述催化剂的摩尔体积比优选125:6mol/L;所述催化剂中铂含量优选为2%;所述Z8与所述溶剂的摩尔体积比优选0.125mol/L;所述反应的温度为80℃;所述反应的反应时间为48h。
In some embodiments, in the method for preparing the polymer represented by formula V, the polymer represented by formula Z8 is The polymer represented by formula S4 is The polymer represented by formula V is The catalyst is a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution; the solvent is a mixed solvent of toluene and acetonitrile; the volume ratio of toluene and acetonitrile is 1:1; the inert atmosphere is an argon atmosphere; the molar ratio of Z8 to S4 is preferably 2.5; the molar volume ratio of Z8 to the catalyst is preferably 125:6 mol/L; the platinum content in the catalyst is preferably 2%; the molar volume ratio of Z8 to the solvent is preferably 0.125 mol/L; the reaction temperature is 80°C; and the reaction time is 48h.
在一些实施方案中,在所述式V所示聚合物的制备方法中,还包括式Z8所示聚合物的制备方法,其包括如下步骤:在溶剂中,在惰性气氛中,将式S5所示化合物、式Z6所示化合物和淬灭试剂S7进行如下所示的反应,制得式Z8所示聚合物,即可,In some embodiments, the method for preparing the polymer of formula V also includes a method for preparing the polymer of formula Z8, which comprises the following steps: in a solvent, in an inert atmosphere, reacting the compound of formula S5, the compound of formula Z6 and the quenching agent S7 as shown below to obtain the polymer of formula Z8, that is,
所述X为卤素、OTf或OTs;Said X is halogen, OTf or OTs;
所述淬灭试剂S7为无机碱(例如KOH)或RH,R定义同上所述;The quenching reagent S7 is an inorganic base (such as KOH) or RH, and R is defined as above;
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述溶剂可为本领域此类反应常用溶剂。所述溶剂优选腈类溶剂。所述溶剂更优选乙腈。In some embodiments, in the method for preparing the polymer represented by formula Z8, the solvent may be a commonly used solvent for such reactions in the art. The solvent is preferably a nitrile solvent. The solvent is more preferably acetonitrile.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述L优选为
或-CH
2-,所述1端与X相连。
In some embodiments, in the method for preparing the polymer represented by formula Z8, L is preferably or -CH 2 -, and the 1 end is connected to X.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述
优选为2-甲基恶唑 啉。
In some embodiments, in the method for preparing the polymer represented by formula Z8, the 2-Methyloxazoline is preferred.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述X优选为Br、Cl或OTs。In some embodiments, in the method for preparing the polymer represented by formula Z8, X is preferably Br, Cl or OTs.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述X优选为Br。In some embodiments, in the method for preparing the polymer represented by formula Z8, X is preferably Br.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述X优选为Cl。In some embodiments, in the method for preparing the polymer represented by formula Z8, X is preferably Cl.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述X优选为OTs。In some embodiments, in the method for preparing the polymer represented by formula Z8, X is preferably OTs.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述淬灭试剂S7优选为氢氧化钾的甲醇溶液、
In some embodiments, in the method for preparing the polymer represented by formula Z8, the quenching reagent S7 is preferably a methanol solution of potassium hydroxide,
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述淬灭试剂S7优选为氢氧化钾的甲醇溶液。更优选氢氧化钾浓度为0.5M的甲醇溶液。In some embodiments, in the method for preparing the polymer represented by formula Z8, the quenching reagent S7 is preferably a methanol solution of potassium hydroxide, more preferably a methanol solution with a potassium hydroxide concentration of 0.5M.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述淬灭试剂S7优选为
In some embodiments, in the method for preparing the polymer represented by formula Z8, the quenching reagent S7 is preferably
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述淬灭试剂S7优选为
In some embodiments, in the method for preparing the polymer represented by formula Z8, the quenching reagent S7 is preferably
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述式S5所示化合物与式Z6所示化合物的摩尔比可为本领域此类反应常规。优选为2:1-1:8。更优选1:1或1:4。In some embodiments, in the method for preparing the polymer represented by formula Z8, the molar ratio of the compound represented by formula S5 to the compound represented by formula Z6 can be conventional in the art for such reactions, preferably 2:1-1:8, more preferably 1:1 or 1:4.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,当所述淬灭试剂S7为氢氧化钾的甲醇溶液时,所述式S5所示化合物与淬灭试剂S7的摩尔体积比可为本领域此类反应常规。优选为5-20mol/L。更优选10mol/L。In some embodiments, in the method for preparing the polymer represented by formula Z8, when the quenching agent S7 is a methanol solution of potassium hydroxide, the molar volume ratio of the compound represented by formula S5 to the quenching agent S7 can be conventional in the art for such reactions, preferably 5-20 mol/L, and more preferably 10 mol/L.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,当所述淬灭试剂S7为
时,所述式S5所示化合物与淬灭试剂S7的摩尔比可为本领域此类反应常规。优选为1:2-2:1。更优选1:1。
In some embodiments, in the method for preparing the polymer represented by formula Z8, when the quenching reagent S7 is When the molar ratio of the compound represented by formula S5 to the quenching agent S7 can be conventional in the art for such reactions, preferably 1:2-2:1, and more preferably 1:1.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,当所述淬灭试剂S7为
时,所述式S5所示化合物与淬灭试剂S7的摩尔比可为本领域此类反应常规。优选为1:2-2:1。更优选1:1。
In some embodiments, in the method for preparing the polymer represented by formula Z8, when the quenching reagent S7 is When the molar ratio of the compound represented by formula S5 to the quenching agent S7 can be conventional in the art for such reactions, preferably 1:2-2:1, and more preferably 1:1.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述式S5所示化合物与溶剂的摩尔体积比可为本领域此类反应常规。优选为1:1.5mol/L-1:3mol/L。更优选50:120mol/L。In some embodiments, in the method for preparing the polymer represented by formula Z8, the molar volume ratio of the compound represented by formula S5 to the solvent can be conventional in the art for such reactions, preferably 1:1.5 mol/L-1:3 mol/L, and more preferably 50:120 mol/L.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述反应温度可为本领域此类反应常规。优选为40-120℃。更优选80℃。In some embodiments, in the method for preparing the polymer represented by formula Z8, the reaction temperature may be conventional for such reactions in the art, preferably 40-120°C, more preferably 80°C.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述反应时间可为本领域此类反应常规。优选为12-48小时。更优选24小时。In some embodiments, in the method for preparing the polymer represented by formula Z8, the reaction time may be conventional for such reactions in the art, preferably 12-48 hours, and more preferably 24 hours.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述惰性气氛可为本领域此类反应常规。优选为氮气气氛或氩气气氛。In some embodiments, in the method for preparing the polymer represented by formula Z8, the inert atmosphere may be conventional in the art for such reactions, preferably a nitrogen atmosphere or an argon atmosphere.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述淬灭试剂S7加入的时机可为本领域此类反应常规。优选在反应冷却至室温后加入。更优选在反应冷却至室温后加入搅拌3小时。In some embodiments, in the method for preparing the polymer of formula Z8, the timing of adding the quenching reagent S7 can be conventional in the art for such reactions. Preferably, it is added after the reaction is cooled to room temperature. More preferably, it is added after the reaction is cooled to room temperature and stirred for 3 hours.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述反应还可包括后处理。所述的后处理步骤可为本领域此类反应常规。优选使用乙醇和再生纤维素膜进行渗滤纯化。更优选使用再生纤维素膜(Millipore,截留分子量为1K)进行渗滤纯化。In some embodiments, in the preparation method of the polymer shown in formula Z8, the reaction may further include post-treatment. The post-treatment step may be conventional for such reactions in the art. Preferably, ethanol and regenerated cellulose membranes are used for diafiltration purification. More preferably, regenerated cellulose membranes (Millipore, molecular weight cut-off is 1K) are used for diafiltration purification.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述后处理中,所述式S5所示化合物与乙醇的摩尔体积比可为本领域此类反应常规。优选为5:70mol/L。In some embodiments, in the method for preparing the polymer represented by formula Z8, in the post-treatment, the molar volume ratio of the compound represented by formula S5 to ethanol can be conventional in the art for such reactions, preferably 5:70 mol/L.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述溶剂为乙腈;所述S5所示化合物为
所述淬灭试剂S7为氢氧化钾浓度为0.5M的甲醇溶液;所述式Z8所示聚合物为
所述Z6所示化合物
为2-甲基恶唑啉;所述式S5所示化合物与式Z6所示化合物
的摩尔比为1:4;所述式S5所示化合物与淬灭试剂S7的摩尔体积比为10mol/L;所述式S5所示化合物与溶剂的摩尔体积比为50:120mol/L;所述反应在反应温度为80℃下进行;所述反应时间为24小时;所述惰性气氛为氩气;所述淬灭试剂S7在反应冷却至室温后加入,加入后搅拌3小时。
In some embodiments, in the method for preparing the polymer represented by formula Z8, the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is a methanol solution with a potassium hydroxide concentration of 0.5M; the polymer represented by the formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and the compound represented by formula Z6 The molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:4; the molar volume ratio of the compound represented by formula S5 to the quenching reagent S7 is 10 mol/L; the molar volume ratio of the compound represented by formula S5 to the solvent is 50:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述溶剂为乙腈;所述S5所示化合物为
所述淬灭试剂S7为
所述式Z8所示聚合物为
所述Z6所示化合物
为2-甲基恶唑啉;所述式S5所示化合物与式Z6所示化合物
的摩尔比为1:4;所述式S5所示化合物与淬灭试剂S7的摩尔比为1:1;所述式S5所示化合物与溶剂的摩尔体积比为50:120mol/L;所述反应在反应温度为80℃下进行;所述反应时间为24小时;所述惰性气氛为氩气;所述淬灭试剂S7在反应冷却至室温后加入,加入后搅拌3小时。
In some embodiments, in the method for preparing the polymer represented by formula Z8, the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is The polymer represented by formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and the compound represented by formula Z6 The molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:4; the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:1; the molar volume ratio of the compound represented by formula S5 to the solvent is 50:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述溶剂为乙腈;所述S5所示化合物为
所述淬灭试剂S7为
所述式Z8所示聚合物为
所述Z6所示化合物
为2-甲基恶唑啉;所述式S5所示化合物与式Z6所示化合物
的摩尔比为1:4;所述式S5所示化合物与淬灭试剂S7的摩尔比为1:1;所述式S5所示化合物与溶剂的摩尔体积比为50:120mol/L;所述反应在反应温度为80℃下进行;所述反应时间为24小时;所述惰性气氛为氩气;所述淬灭试剂S7在反应冷却至室温后加入,加入后搅拌3小时。
In some embodiments, in the method for preparing the polymer represented by formula Z8, the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is The polymer represented by formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and the compound represented by formula Z6 The molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:4; the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:1; the molar volume ratio of the compound represented by formula S5 to the solvent is 50:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述溶剂为乙腈;所述S5所示化合物为
所述淬灭试剂S7为
所述式Z8所示聚合物为
所述Z6所示化合物
为2-甲基恶唑啉;所述式S5所示化合物与式Z6所示化合物
的摩尔比为1:1;所述式S5所示化合物与淬灭试剂S7的摩尔比为1:1;所述式S5所示化合物与溶剂的摩尔体积比为50:120mol/L;所述反应在反应温度为80℃下进行;所述反应时间为24小时;所述惰性气氛为氩气;所述淬灭试剂S7在反应冷却至室温后加入,加入后搅拌3小时。
In some embodiments, in the method for preparing the polymer represented by formula Z8, the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is The polymer represented by formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and the compound represented by formula Z6 The molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:1; the molar volume ratio of the compound represented by formula S5 to the solvent is 50:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
在一些实施方案中,在所述的式Z8所示聚合物的制备方法中,所述溶剂为乙腈;所述S5所示化合物为
所述淬灭试剂S7为氢氧化钾浓度为0.5M的甲醇溶液;所述式Z8所示聚合物为
所述Z6所示化合物
为2-甲基恶唑啉;所述式S5所示化合物与式Z6
所示化合物的摩尔比为1:1;所述式S5所示化合物与淬灭试剂S7的摩尔体积比为2.5mol/L;所述式S5所示化合物与溶剂的摩尔体积比为12.5:120mol/L;所述反应在反应温度为80℃下进行;所述反应时间为24小时;所述惰性气氛为氩气;所述淬灭试剂S7在反应冷却至室温后加入,加入后搅拌3小时。
In some embodiments, in the method for preparing the polymer represented by formula Z8, the solvent is acetonitrile; the compound represented by S5 is The quenching reagent S7 is a methanol solution with a potassium hydroxide concentration of 0.5M; the polymer represented by the formula Z8 is The compound represented by Z6 is 2-methyloxazoline; the compound represented by formula S5 and formula Z6 The molar ratio of the compounds shown is 1:1; the molar volume ratio of the compound shown in formula S5 and the quenching reagent S7 is 2.5 mol/L; the molar volume ratio of the compound shown in formula S5 and the solvent is 12.5:120 mol/L; the reaction is carried out at a reaction temperature of 80°C; the reaction time is 24 hours; the inert atmosphere is argon; the quenching reagent S7 is added after the reaction is cooled to room temperature and stirred for 3 hours after addition.
本发明提供了一种式Z8所示聚合物:The present invention provides a polymer represented by formula Z8:
本发明提供了一种式Z8所示聚合物的制备方法,其包括如下步骤:在溶剂中,在惰性气氛中,将式S5所示化合物、式Z6所示化合物和淬灭试剂S7进行如下所示的反应,制得式Z8所示聚合物,即可,The present invention provides a method for preparing a polymer represented by formula Z8, which comprises the following steps: in a solvent and in an inert atmosphere, reacting a compound represented by formula S5, a compound represented by formula Z6 and a quenching agent S7 as shown below to obtain a polymer represented by formula Z8, that is,
其中,R、X、淬灭试剂S7、
L和
定义以及反应条件例如反应温度、反应时间、各反应物摩尔比值、反应操作等同前所述。
Among them, R, X, quenching reagent S7, L and The definitions and reaction conditions such as reaction temperature, reaction time, molar ratio of each reactant, reaction operation and the like are the same as described above.
如无特别说明,本发明所用术语具有如下含义:Unless otherwise specified, the terms used in the present invention have the following meanings:
基团末端的“-”是指该基团通过该位点与分子其余部分相连。例如,-CN是指氰基。A "-" at the end of a group means that the group is attached to the rest of the molecule through that site. For example, -CN refers to a cyano group.
术语“烷基”是指具有指定碳原子数的、直链或支链的、饱和的一价烃基。例如,C
1-C
6烷基包括但不限于:甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、正己基等。
The term "alkyl" refers to a linear or branched, saturated, monovalent hydrocarbon group having a specified number of carbon atoms. For example, C1 - C6 alkyl includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, etc.
术语“烷氧基”是指基团R
X-O-,R
X的定义同术语“烷基”。烷氧基包括但不限于:甲氧基、乙氧基、正丙氧基、异丙氧基等。
The term "alkoxy" refers to the group R X -O-, where R X is defined as the term "alkyl". Alkoxy includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, and the like.
术语“烷硫基”是指基团R
X-S-,R
X的定义同术语“烷基”。烷硫基包括但不限于:甲硫基、乙硫基、正丙硫基、异丙硫基等。
The term "alkylthio" refers to the group R X -S-, where R X is defined as the term "alkyl". Alkylthio includes, but is not limited to, methylthio, ethylthio, n-propylthio, isopropylthio, and the like.
术语“芳基”是指具有指定碳原子数(例如,C
6-C
10)的、环状的、不饱和的一价烃基,其为单环或多环(例如,2个或3个),为多环时,单环之间共用两个原子和一根键,且至少一个环具有芳香性。芳基通过具有芳香性的环或不具有芳香性的环与分子其余部分相连。芳基包括但不限于:苯基、萘基、
等。
The term "aryl" refers to a cyclic, unsaturated, monovalent hydrocarbon group with a specified number of carbon atoms (e.g., C 6 -C 10 ), which is a single ring or multiple rings (e.g., 2 or 3). When it is a multiple ring, the single rings share two atoms and a bond, and at least one ring is aromatic. The aryl group is connected to the rest of the molecule through an aromatic ring or a non-aromatic ring. Aryl groups include, but are not limited to, phenyl, naphthyl, wait.
术语“杂芳基”是指具有指定环原子数(例如,5-10元)的、指定杂原子数(例如,1个、2个或3个)的、指定杂原子种类(N、O和S中的一种或多种)的、环状的、不饱和的一价基团,其为单环或多环,单环之间共用两个原子和一根键,且至少一个环具有芳香性。杂芳基通过碳原子或杂原子与分子其余部分相连;杂芳基通过具有杂原子的环或不具有杂原子的环与分子其余部分相连;杂芳基通过具有芳香性的环或不具有芳香性的环与分子其余部分相连。杂芳基包括但不限于:
等。
The term "heteroaryl" refers to a cyclic, unsaturated, monovalent group having a specified number of ring atoms (e.g., 5-10 members), a specified number of heteroatoms (e.g., 1, 2, or 3), a specified type of heteroatom (one or more of N, O, and S), which is a single ring or multiple rings, with two atoms and a bond shared between the single rings, and at least one ring being aromatic. A heteroaryl group is attached to the rest of the molecule through a carbon atom or a heteroatom; a heteroaryl group is attached to the rest of the molecule through a ring with heteroatoms or a ring without heteroatoms; a heteroaryl group is attached to the rest of the molecule through a ring with aromatic properties or a ring without aromatic properties. Heteroaryl groups include, but are not limited to: wait.
在不违背本领域常识的基础上,上述各优选条件,可任意组合,即得本发明各较佳实例。Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.
本发明所用试剂和原料均市售可得。The reagents and raw materials used in the present invention are commercially available.
本发明的积极进步效果在于:本申请聚合物可以在溶液中自组装成囊泡结构,并且囊泡稳定性好。本申请制备方法合成步骤少,反应条件温和,收率高,聚合物分散性低,重复性好,实现了精确的分子量控制和对封端基团,聚合物疏水嵌段与亲水嵌段之间连接基团的多样化修饰等优点。The positive progress of the present invention is that the polymer of the present invention can self-assemble into a vesicle structure in a solution, and the vesicle has good stability. The preparation method of the present invention has the advantages of fewer synthesis steps, mild reaction conditions, high yield, low polymer dispersibility, good repeatability, and accurate molecular weight control and diversified modification of the end-capping group and the connecting group between the hydrophobic block and the hydrophilic block of the polymer.
实例中各试剂纯度及生产厂家信息如下:The purity and manufacturer information of each reagent in the example are as follows:
实施例1三嵌段聚合物P1的合成Example 1 Synthesis of triblock polymer P1
三嵌段聚合物P1的合成路线如下:The synthetic route of triblock polymer P1 is as follows:
步骤1,合成预聚物S4-1:在氮气保护下用移液枪向schlenk瓶加入21mL S1(0.956g/mL,296.62g/mol,67.68mmol),上口用橡胶塞密封,然后用注射器加入1.5mL的1,1,3,3-四甲基二硅氧烷S2(0.76g/mL,134.33g/mol,8.49mmol),S1与S2物质的量比为8︰1,S1可以稍过量,氩气除氧三次。升温至55℃,再用微量进样器加入76.5μL三氟甲磺酸S3(1.696g/mL,150.08g/mol,0.86mmol)。55℃下反应72h。反应完毕后,冷却至室温,将产物溶于200ml乙醚,在分液漏斗中用去离子水多次萃取体系中的三氟甲磺酸。加入无水硫酸镁搅拌约1h除去水分,过滤。旋蒸除去乙醚。在120℃真空干燥约8h,得到硅氢键封端的PDMS预聚物S4(19.7g,93%)。其结构及其聚合度由核磁氢谱积分确定为35。Step 1, synthesis of prepolymer S4-1: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 1.5 mL of 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 8.49 mmol) with a syringe. The molar ratio of S1 to S2 is 8:1. S1 can be slightly excessive, and argon gas is used for deoxygenation three times. Heat to 55°C, and then add 76.5 μL trifluoromethanesulfonic acid S3 (1.696 g/mL, 150.08 g/mol, 0.86 mmol) with a microinjector. React at 55°C for 72 hours. After the reaction is completed, cool to room temperature, dissolve the product in 200 ml of ether, and extract the trifluoromethanesulfonic acid in the system with deionized water in a separatory funnel several times. Add anhydrous magnesium sulfate and stir for about 1 hour to remove moisture, and filter. Remove the ether by rotary evaporation. Dry in vacuum at 120°C for about 8 hours to obtain a PDMS prepolymer S4 (19.7 g, 93%) terminated with a silicon-hydrogen bond. Its structure and degree of polymerization were determined to be 35 by the integral of the H-NMR spectrum.
1H NMR(500MHz,CDCl3)δ4.71-4.70(m,1H),0.19-0.07(m,111.77H);1/111.77=2/(6n+12),n=35,Mn=3200g/mol.
1 H NMR (500 MHz, CDCl3) δ 4.71-4.70 (m, 1H), 0.19-0.07 (m, 111.77H); 1/111.77 = 2/(6n+12), n = 35, Mn = 3200 g/mol.
GPC(DMF):PDI 1.101.GPC(DMF):PDI 1.101.
步骤2,合成预聚物Z8-1:在氩气中将干燥的乙烯基化合物S5-1(7.6g,152.62g/mol,50mmol)与反应原料Z6-1(17g,85.1g/mol,200mmol)混合溶于干燥乙腈(120mL)中。80℃下反应24h。核磁氢谱确定反应完成。待反应完全后,将混合物冷却至室温,然后将5ml 0.5M含有氢氧化钾S7-1(0.48g)的甲醇溶液加入到混合物中终止反应,并搅拌3小时。减压除去溶剂后,将产物溶于100ml二氯甲烷,过滤除去残留无机盐及过量氢氧化钾。减压除去溶剂,并将所得聚合物在真空下干燥,得到乙烯基封端的PMOXA预聚物Z8-1(20.0g,收率91%)。其结构及其聚合度由核磁氢谱积分确定。Step 2, synthesis of prepolymer Z8-1: dry vinyl compound S5-1 (7.6 g, 152.62 g/mol, 50 mmol) and reaction raw material Z6-1 (17 g, 85.1 g/mol, 200 mmol) were mixed and dissolved in dry acetonitrile (120 mL) in argon. React at 80 ° C for 24 h. The reaction was completed by nuclear magnetic hydrogen spectrum. After the reaction was complete, the mixture was cooled to room temperature, and then 5 ml of 0.5 M methanol solution containing potassium hydroxide S7-1 (0.48 g) was added to the mixture to terminate the reaction, and stirred for 3 hours. After removing the solvent under reduced pressure, the product was dissolved in 100 ml of dichloromethane, and the residual inorganic salts and excess potassium hydroxide were filtered out. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain a vinyl-terminated PMOXA prepolymer Z8-1 (20.0 g, yield 91%). Its structure and degree of polymerization were determined by nuclear magnetic hydrogen spectrum integration.
1H NMR(500MHz,CDCl3)δ7.45-7.32(m,2H),7.25-7.10(m,2H),6.75-6.62(m,1H),5.82-5.63(m, 1H),5.35-5.16(m,1H),4.70-4.45(m,2H),3.85-3.65(m,15.67H),2.25-2.00(m,10.82H),1/3m=1/10.82,m=3.6.Mn=440g/mol
1 H NMR (500MHz,CDCl3)δ7.45-7.32(m,2H),7.25-7.10(m,2H),6.75-6.62(m,1H),5.82-5.63(m, 1H),5.35-5.16(m,1H),4.70-4.45(m,2H),3.85-3.65(m,15.67H),2.25-2.00(m,10.82H),1/3m=1/10.82,m=3.6.Mn=440g/mol
GPC(DMF):PDI 1.197.GPC(DMF):PDI 1.197.
步骤3,三嵌段P1合成:在氩气中将反应原料S4-1(3.2g,3200g/mol,1mmol)与干燥的反应原料Z8-1(1.1g,440g/mol,2.5mmol)溶于20ml干燥的甲苯乙腈混合溶剂(1/1)中,待充分溶解后,加入120uL Karstedt Catalyst(in xylene,Pt~2%),后升温至80℃,80℃下搅拌24h,待反应完全后,将混合物冷却至室温,过滤,固体用乙醚(10mL)洗三次后,将产物溶于100ml乙醇中,并用超过600ml的乙醇通过再生纤维素膜(Millipore,截留分子量为1KDa)渗滤纯化。减压除去溶剂,并将所得聚合物在真空下干燥,得到三嵌段HO-PMOXA-PDMS-PMOXA-OH聚合物P1(1.5g,收率42%)。Step 3, synthesis of triblock P1: In argon, the reaction raw material S4-1 (3.2 g, 3200 g/mol, 1 mmol) and the dry reaction raw material Z8-1 (1.1 g, 440 g/mol, 2.5 mmol) were dissolved in 20 ml of dry toluene acetonitrile mixed solvent (1/1). After sufficient dissolution, 120 uL Karstedt Catalyst (in xylene, Pt~2%) was added, and then the temperature was raised to 80°C and stirred at 80°C for 24 h. After the reaction was complete, the mixture was cooled to room temperature and filtered. The solid was washed three times with ether (10 mL), and the product was dissolved in 100 ml of ethanol and purified by filtration through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 1 KDa) with more than 600 ml of ethanol. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain triblock HO-PMOXA-PDMS-PMOXA-OH polymer P1 (1.5 g, yield 42%).
1H NMR(500MHz,CDCl3)δ7.20-7.07(m,2H),3.57-3.17(m,1H),2.23-1.92(m,1H),0.03-0.00(m,8.3H).Mn=3604g/mol
1 H NMR (500MHz,CDCl3)δ7.20-7.07(m,2H),3.57-3.17(m,1H),2.23-1.92(m,1H),0.03-0.00(m,8.3H).Mn=3604g/mol
GPC(DMF):1.129.GPC(DMF):1.129.
实施例2三嵌段聚合物P2的合成Example 2 Synthesis of triblock polymer P2
三嵌段聚合物P2的合成路线如下:The synthetic route of triblock polymer P2 is as follows:
步骤1,合成预聚物S4-1:在氮气保护下用移液枪向schlenk瓶加入21mL S1(0.956g/mL,296.62g/mol,67.68mmol),上口用橡胶塞密封,然后用注射器加入1.5mL的1,1,3,3-四甲基二硅氧烷S2(0.76g/mL,134.33g/mol,8.49mmol),S1与S2物质的量比为8︰1,S1可以稍过量,除氧三次。升温至55℃,再用微量进样器加入76.5μL三氟甲磺酸S3(1.696g/mL,150.08g/mol,0.86mmol)。55℃下反应72h。反应完毕后,冷却至室温,将产物溶于200mL乙醚,在分液漏斗中用去离子水多次萃取体系中的三氟甲磺酸。加入无水硫酸镁搅拌约1h除去水分,过滤。旋蒸除去乙醚。在120℃真空干燥约8h,得到硅氢键封端的PDMS预聚物S4(19.7g,93%)。其结构及其聚合度由核磁氢谱积分确定为35。Step 1, synthesis of prepolymer S4-1: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 1.5 mL of 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 8.49 mmol) with a syringe. The molar ratio of S1 to S2 is 8:1. S1 can be slightly excessive and deoxygenated three times. Heat to 55°C, and then add 76.5 μL trifluoromethanesulfonic acid S3 (1.696 g/mL, 150.08 g/mol, 0.86 mmol) with a microinjector. React at 55°C for 72 hours. After the reaction is completed, cool to room temperature, dissolve the product in 200 mL of ether, and extract the trifluoromethanesulfonic acid in the system with deionized water in a separatory funnel several times. Add anhydrous magnesium sulfate and stir for about 1 hour to remove moisture, and filter. Remove the ether by rotary evaporation. Dry under vacuum at 120°C for about 8 hours to obtain a silicon-hydrogen bond-terminated PDMS prepolymer S4 (19.7 g, 93%). Its structure and degree of polymerization were determined to be 35 by nuclear magnetic hydrogen spectrum integration.
1H NMR(500MHz,CDCl3)δ4.71-4.70(m,1H),0.19-0.07(m,111.77H);1/111.77=2/(6n+12),n=35,Mn=3200g/mol.
1 H NMR (500 MHz, CDCl3) δ 4.71-4.70 (m, 1H), 0.19-0.07 (m, 111.77H); 1/111.77 = 2/(6n+12), n = 35, Mn = 3200 g/mol.
GPC(DMF):PDI 1.101.GPC(DMF):PDI 1.101.
步骤2,合成预聚物Z8-2:在氩气中将干燥的乙烯基化合物S5-2(50mmol)(6.1g,120.99g/mol,50mmol)与反应原料Z6-1(17g,85.1g/mol,200mmol)混合溶于干燥乙腈(120mL)中。80℃下反应24h。核磁氢谱确定反应完成。待反应完全后,将混合物冷却至室温,然后通过加入S7-2(14.7g,147.1g/mol,50mmol)终止反应,并搅拌3小时。减压除去溶剂后,将产物溶于100ml去离子水,过滤除去残留S7-2。减压除去溶剂,并将所得聚合物在真空下干燥,得到乙烯基封端的PMOXA预聚物Z8-2(19.0g,79.2%)。其结构及其聚合度由核磁氢谱积分确定。Step 2, synthesis of prepolymer Z8-2: dry vinyl compound S5-2 (50mmol) (6.1g, 120.99g/mol, 50mmol) and reaction raw material Z6-1 (17g, 85.1g/mol, 200mmol) were mixed and dissolved in dry acetonitrile (120mL) in argon. React at 80°C for 24h. The reaction was completed by H NMR. After the reaction was complete, the mixture was cooled to room temperature, and then the reaction was terminated by adding S7-2 (14.7g, 147.1g/mol, 50mmol) and stirred for 3 hours. After removing the solvent under reduced pressure, the product was dissolved in 100ml of deionized water and the residual S7-2 was removed by filtration. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain a vinyl-terminated PMOXA prepolymer Z8-2 (19.0g, 79.2%). Its structure and degree of polymerization were determined by H NMR spectrum integration.
1H NMR(500MHz,CDCl3)δ7.86-7.78(m,1.19H),7.78-7.64(m,1.35H),7.45-7.30(m,2.04H),7.25-7.00(m,1.82H),6.75-6.58(m,1.00H),5.81-5.63(m,1H),5.33-5.15(m,1H),4.78-4.45(m,2.22H),4.00-3.20(m,14.49H),2.30-1.90(m,11.00).m=3.6.Mn=493g/mol
1 H NMR (500MHz,CDCl3)δ7.86-7.78(m,1.19H),7.78-7.64(m,1.35H),7.45-7.30(m,2.04H),7.25-7.00(m,1.82H),6.75-6.58(m,1.00H),5.81-5.63(m,1H),5.33-5.15(m,1H),4.78-4.45(m,2.22H),4.00-3.20(m,14.49H),2.30-1.90(m,11.00).m=3.6.Mn=493g/mol
GPC(DMF):PDI=1.056.GPC (DMF): PDI = 1.056.
步骤3,三嵌段P2合成:在氩气中将反应原料S4-1(3.2g,3200g/mol,1mmol)与干燥的反应原料Z8-2(1.2g,493g/mol,2.5mmol)溶于20ml干燥的甲苯/乙腈混合溶剂(1/1)中,室温下待原料充分溶解后,加入120uL Karstedt催化剂(in xylene,Pt~2%),升温至80℃,80℃下搅拌48h,待反应完全后,将混合物冷却至室温,过滤,固体用乙醚(10mL)洗三次后,将产物溶于100ml乙醇中,并用超过600ml的乙醇通过再生纤维素膜(Millipore,截留分子量为1K)渗滤纯化。减压除去溶剂,并将所得聚合物在真空下干燥,得到三嵌段PMOXA-PDMS-PMOXA聚合物P2(1.2g,收率32.4%)。Step 3, synthesis of triblock P2: In argon, the reaction raw material S4-1 (3.2 g, 3200 g/mol, 1 mmol) and the dry reaction raw material Z8-2 (1.2 g, 493 g/mol, 2.5 mmol) were dissolved in 20 ml of dry toluene/acetonitrile mixed solvent (1/1). After the raw materials were fully dissolved at room temperature, 120 uL Karstedt catalyst (in xylene, Pt~2%) was added, the temperature was raised to 80°C, and stirred at 80°C for 48 h. After the reaction was complete, the mixture was cooled to room temperature and filtered. The solid was washed three times with ether (10 mL), and the product was dissolved in 100 ml of ethanol and purified by filtration through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 1K) with more than 600 ml of ethanol. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain triblock PMOXA-PDMS-PMOXA polymer P2 (1.2 g, yield 32.4%).
1H NMR(500MHz,CDCl3)δ7.86-7.75(m,4H),7.75-7.63(m,4H),3.65-3.15(m,8H),2.22-1.82 (m,6.70H),0.15-0.00(m,42.65H).Mn=3710g/mol
1 H NMR (500MHz,CDCl3)δ7.86-7.75(m,4H),7.75-7.63(m,4H),3.65-3.15(m,8H),2.22-1.82(m,6.70H),0.15-0.00(m,42.65H).Mn=3710g/mol
GPC(DMF):PDI 1.131.GPC(DMF):PDI 1.131.
实施例3五嵌段聚合物P3的合成Example 3 Synthesis of Pentablock Polymer P3
五嵌段聚合物P3的合成路线如下:The synthetic route of the pentablock polymer P3 is as follows:
步骤1,合成预聚物S4-2:在氮气保护下用移液枪向schlenk瓶加入21mL S1(0.956g/mL,296.62g/mol,67.68mmol),上口用橡胶塞密封,然后用注射器加入1.7mL的1,1,3,3-四甲基二硅氧烷S2(0.76g/mL,134.33g/mol,9.67mmol),S1与S2物质的量比为7︰1,S1可以稍过量,氩气除氧三次。升温至55℃,再用微量进样器加入76.5μL三氟甲磺酸S3(1.696g/mL,150.08g/mol,0.86mmol)。55℃下反应72h。反应完毕后,冷却至室温,将产物溶于200ml乙醚,在分液漏斗中用去离子水多次萃取体系中的三氟甲磺酸。加入无水硫酸镁搅拌约1h除去水分,过滤。旋蒸除去乙醚。在120℃真空干燥约8h,得到硅氢键封端的PDMS预聚物S4(18.7g,收率89%)。其结构及其聚合度由核磁氢谱积分确定为30.0,如下所示。Step 1, synthesis of prepolymer S4-2: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 1.7 mL 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 9.67 mmol) with a syringe. The molar ratio of S1 to S2 is 7:1. S1 can be slightly excessive, and argon gas is used for deoxygenation three times. Heat to 55°C, and then add 76.5 μL trifluoromethanesulfonic acid S3 (1.696 g/mL, 150.08 g/mol, 0.86 mmol) with a microinjector. React at 55°C for 72 hours. After the reaction is completed, cool to room temperature, dissolve the product in 200 ml of ether, and extract the trifluoromethanesulfonic acid in the system with deionized water in a separatory funnel several times. Add anhydrous magnesium sulfate and stir for about 1 hour to remove moisture, and filter. Remove the ether by rotary evaporation. Dry in vacuum at 120°C for about 8 hours to obtain a silicon-hydrogen bond-terminated PDMS prepolymer S4 (18.7 g, yield 89%). Its structure and degree of polymerization were determined to be 30.0 by nuclear magnetic hydrogen spectrum integration, as shown below.
1H NMR(500MHz,CDCl3)δ4.71-4.70(m,1H),0.19-0.07(m,89.58H),根据H-NMR核磁积分计算PDMS聚合度,1/89.58=2/(6n+12)n=29.94,Mn=2354g/mol;
1 H NMR (500 MHz, CDCl3) δ 4.71-4.70 (m, 1H), 0.19-0.07 (m, 89.58H), the degree of polymerization of PDMS was calculated based on the H-NMR nuclear magnetic integration, 1/89.58 = 2/(6n+12)n = 29.94, Mn = 2354 g/mol;
GPC(DMF):PDI 1.190.GPC(DMF):PDI 1.190.
步骤2合成预聚物Z8-3:在氩气中将干燥的乙烯基化合物S5-2(6.1g,120.99g/mol,50mmol)与反应原料Z6-1(17g,85.1g/mol,200mmol)混合溶于干燥乙腈(120mL)中。80℃下反应24h。核磁氢谱确定反应完成。待反应完全后,将混合物冷却至室温,然后通过加入S7-3(7.5g,150.2g/mol,50mmol)终止反应,并搅拌3小时。减压除去溶剂,并将所得聚合物在真空下干燥,得到乙烯基封端的PMOXA预聚物Z8-3(19.0g,79.2%)。其结构及其聚合度由核磁氢谱积分确定。Step 2 Synthesis of prepolymer Z8-3: Mix the dried vinyl compound S5-2 (6.1 g, 120.99 g/mol, 50 mmol) and the reaction raw material Z6-1 (17 g, 85.1 g/mol, 200 mmol) in dry acetonitrile (120 mL) in argon. React at 80°C for 24 h. The nuclear magnetic hydrogen spectrum confirms that the reaction is complete. After the reaction is complete, the mixture is cooled to room temperature, and then the reaction is terminated by adding S7-3 (7.5 g, 150.2 g/mol, 50 mmol) and stirred for 3 hours. The solvent is removed under reduced pressure, and the resulting polymer is dried under vacuum to obtain a vinyl-terminated PMOXA prepolymer Z8-3 (19.0 g, 79.2%). Its structure and degree of polymerization are determined by nuclear magnetic hydrogen spectrum integration.
1H NMR(500MHz,CDCl3)δ6.10-4.88(m,3H),4.53-3.80(m,5.87H),3.70-3.16(m,24.98H),2.49-2.46(m,1.13H),2.00-1.84(m,3.06H).根据H-NMR核磁积分计算PMOXA聚合度3.06/1=3m/1m=1.0Mn=289g/mol
1 H NMR (500MHz, CDCl3) δ6.10-4.88 (m, 3H), 4.53-3.80 (m, 5.87H), 3.70-3.16 (m, 24.98H), 2.49-2.46 (m, 1.13H), 2.00-1.84 (m, 3.06H). PMOXA degree of polymerization calculated based on H-NMR nuclear magnetic integration is 3.06/1 = 3m/1m = 1.0Mn = 289g/mol
GPC(DMF):PDI 1.10.GPC(DMF):PDI 1.10.
步骤3,三嵌段P3合成:在氩气中将反应原料S4-2(2.3g,2354g/mol,1mmol)与干燥的反应原料Z8-3(0.7g,289g/mol,2.5mmol))溶于20ml干燥的甲苯/乙腈混合溶剂(1/1)中,室温下待原料充分溶解后,加入120uL Karstedt催化剂(in xylene,Pt~2%),升温至80℃,80℃下搅拌48h,待反应完全后,将混合物冷却至室温,过滤,固体用乙醚(10mL)洗三次后,将产物溶于100ml乙醇中,并用超过600ml的乙醇通过再生纤维素膜(Millipore,截留分子量为1K)渗滤纯化。减压除去溶剂,并将所得聚合物在真空下干燥,得到五嵌段PEG-PMOXA-PDMS-PMOXA-PEG(3-1-30-1-3)聚合物P3(1.1g,收率38%)。Step 3, synthesis of triblock P3: In argon, the reaction raw material S4-2 (2.3 g, 2354 g/mol, 1 mmol) and the dry reaction raw material Z8-3 (0.7 g, 289 g/mol, 2.5 mmol)) were dissolved in 20 ml of dry toluene/acetonitrile mixed solvent (1/1). After the raw materials were fully dissolved at room temperature, 120 uL of Karstedt catalyst (in xylene, Pt~2%) was added, the temperature was raised to 80°C, and stirred at 80°C for 48 h. After the reaction was complete, the mixture was cooled to room temperature and filtered. The solid was washed three times with ether (10 mL), and the product was dissolved in 100 ml of ethanol and purified by filtration through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 1K) with more than 600 ml of ethanol. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain pentablock PEG-PMOXA-PDMS-PMOXA-PEG (3-1-30-1-3) polymer P3 (1.1 g, yield 38%).
1H NMR(500MHz,CDCl3)δ3.82-3.47(m,17.23H),2.35-2.08(m,3.00H),0.45(m,0.89H),0.07(198.0H).Mn=2932g/mol;
1 H NMR (500 MHz, CDCl3) δ 3.82-3.47 (m, 17.23H), 2.35-2.08 (m, 3.00H), 0.45 (m, 0.89H), 0.07 (198.0H). Mn = 2932 g/mol;
GPC(DMF):PDI 1.21GPC(DMF):PDI 1.21
实施例4五嵌段聚合物P4的合成Example 4 Synthesis of Pentablock Polymer P4
五嵌段聚合物P4的合成路线如下:The synthetic route of the pentablock polymer P4 is as follows:
步骤1,合成预聚物S4-3:在氮气保护下用移液枪向schlenk瓶加入21mL S1(0.956g/mL,296.62g/mol,67.68mmol),上口用橡胶塞密封,然后用注射器加入2.4mL的1,1,3,3-四甲基二硅氧烷S2(0.76g/mL,134.33g/mol,13.54mmol),S1与S2物质的量比为5︰1,S1可以稍过量,氩气除氧三次。升温至55℃,再用微量进样器加入76.5μL三氟甲磺酸S3(1.696g/mL,150.08g/mol,0.86mmol)。55℃下反应72h。反应完毕后,冷却至室温,将产物溶于200ml乙醚,在分液漏斗中用去离子水多次萃取体系中的三氟甲磺酸。加入无水硫酸镁搅拌约1h除去水分,过滤。旋蒸除去乙醚。在120℃真空干燥约8h,得到硅氢键封端的PDMS预聚物S4-3(19.7g,收率90%)。其结构及其聚合度由核磁氢谱积分确定为20。Step 1, synthesis of prepolymer S4-3: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 2.4 mL 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 13.54 mmol) with a syringe. The molar ratio of S1 to S2 is 5:1. S1 can be slightly excessive, and argon gas is used for deoxygenation three times. Heat to 55°C, and then add 76.5 μL trifluoromethanesulfonic acid S3 (1.696 g/mL, 150.08 g/mol, 0.86 mmol) with a microinjector. React at 55°C for 72 hours. After the reaction is completed, cool to room temperature, dissolve the product in 200 ml of ether, and extract the trifluoromethanesulfonic acid in the system with deionized water in a separatory funnel several times. Add anhydrous magnesium sulfate and stir for about 1 hour to remove moisture, and filter. Remove the ether by rotary evaporation. Dry under vacuum at 120°C for about 8 hours to obtain a silicon-hydrogen bond-terminated PDMS prepolymer S4-3 (19.7 g, yield 90%). Its structure and degree of polymerization were determined to be 20 by nuclear magnetic hydrogen spectrum integration.
1H NMR(500MHz,CDCl3)δ4.72-4.69(m,2H),0.19-0.07(m,131.24H);2/131.24=2/(6n+12),n=20,Mn=1628g/mol.
1 H NMR (500 MHz, CDCl3) δ 4.72-4.69 (m, 2H), 0.19-0.07 (m, 131.24H); 2/131.24 = 2/(6n+12), n = 20, Mn = 1628 g/mol.
GPC(DMF):PDI 1.181.GPC(DMF):PDI 1.181.
步骤2,合成预聚物Z8-4:在氩气中将干燥的乙烯基化合物S5-1(7.6g,152.62g/mol,50mmol)与反应原料Z6-1(4.3g,85.1g/mol,50mmol)混合溶于干燥乙腈(120mL)中。80℃下反应24h。核磁氢谱确定反应完成。待反应完全后,将混合物冷却至室温,然后通过加入S7-3(7.5g,150.2g/mol,50mmol)终止反应,并搅拌3小时。减压除去溶剂后,将产物溶于100ml二氯甲烷,过滤除去残留无机盐及过量氢氧化钾。减压除去溶剂,并将所得聚合物在真空下干燥,得到乙烯基封端的PMOXA预 聚物Z8-4(16.1g,收率88%)。其结构及其聚合度由核磁氢谱积分确定。Step 2, synthesis of prepolymer Z8-4: dry vinyl compound S5-1 (7.6g, 152.62g/mol, 50mmol) and reaction raw material Z6-1 (4.3g, 85.1g/mol, 50mmol) were mixed and dissolved in dry acetonitrile (120mL) in argon. React at 80°C for 24h. The reaction was completed by H NMR spectrum. After the reaction was complete, the mixture was cooled to room temperature, and then the reaction was terminated by adding S7-3 (7.5g, 150.2g/mol, 50mmol) and stirred for 3 hours. After the solvent was removed under reduced pressure, the product was dissolved in 100ml of dichloromethane, and the residual inorganic salts and excess potassium hydroxide were filtered out. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain vinyl-terminated PMOXA prepolymer Z8-4 (16.1g, yield 88%). Its structure and degree of polymerization were determined by H NMR spectrum integration.
1H NMR(500MHz,CDCl3)δ7.60-7.20(m,4H),6.69-6.59(m,1H),5.73-5.69(m,1H),5.25-5.17(m,1H),4.06(s,2H),3.66-3.40(m,19.63H),2.20-1.95(m,3.44H),1/3m=1/3.44,m=1.1.Mn=366g/mol
1 H NMR (500MHz,CDCl3)δ7.60-7.20(m,4H),6.69-6.59(m,1H),5.73-5.69(m,1H),5.25-5.17(m,1H),4.06(s,2H),3.66-3.40(m,19.63H),2.20-1.95(m,3.44H),1/3m=1/3.44,m=1.1.Mn=366g/mol
GPC(DMF):PDI 1.197.GPC(DMF):PDI 1.197.
步骤3,三嵌段P4合成:在氩气中将反应原料S4-3(1.6g,1628g/mol,1mmol)与干燥的反应原料Z8-4(0.92g,366g/mol,2.5mmol)溶于20ml干燥的甲苯/乙腈混合溶剂(1/1)中,室温下待原料充分溶解后,加入120uL Karstedt催化剂(in xylene,Pt~2%),升温至80℃,80℃下搅拌48h,待反应完全后,将混合物冷却至室温,过滤,固体用乙醚(10mL)洗三次后,将产物溶于100ml乙醇中,并用超过600ml的乙醇通过再生纤维素膜(Millipore,截留分子量为1K)渗滤纯化。减压除去溶剂,并将所得聚合物在真空下干燥,得到五嵌段PEG-PMOXA-PDMS-PMOXA-PEG(3-1.1-20-1.1-3)聚合物P4(0.9g,收率39%)。Step 3, synthesis of triblock P4: In argon, the reaction raw material S4-3 (1.6 g, 1628 g/mol, 1 mmol) and the dry reaction raw material Z8-4 (0.92 g, 366 g/mol, 2.5 mmol) were dissolved in 20 ml of dry toluene/acetonitrile mixed solvent (1/1). After the raw materials were fully dissolved at room temperature, 120 uL of Karstedt catalyst (in xylene, Pt~2%) was added, the temperature was raised to 80°C, and stirred at 80°C for 48 h. After the reaction was complete, the mixture was cooled to room temperature and filtered. The solid was washed three times with ether (10 mL), and the product was dissolved in 100 ml of ethanol and purified by filtration through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 1K) with more than 600 ml of ethanol. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain pentablock PEG-PMOXA-PDMS-PMOXA-PEG (3-1.1-20-1.1-3) polymer P4 (0.9 g, yield 39%).
1H NMR(500MHz,CDCl3)δ7.50-7.00(m,1H),4.70-4.40(m,0.29H),3.80-3.40(m,19.70H),2.70-2.20(m,6.00H),0.07-0.00(m,121.10H).Mn=2316g/mol;
1 H NMR (500 MHz, CDCl3) δ 7.50-7.00 (m, 1H), 4.70-4.40 (m, 0.29H), 3.80-3.40 (m, 19.70H), 2.70-2.20 (m, 6.00H), 0.07-0.00 (m, 121.10H). Mn = 2316 g/mol;
GPC(DMF):PDI 1.218.GPC(DMF):PDI 1.218.
实施例5五嵌段聚合物P5的合成Example 5 Synthesis of Pentablock Polymer P5
五嵌段聚合物P5的合成路线如下:The synthetic route of the pentablock polymer P5 is as follows:
步骤1,合成预聚物S4-3:在氮气保护下用移液枪向schlenk瓶加入21mL S1(0.956g/mL,296.62g/mol,67.68mmol),上口用橡胶塞密封,然后用注射器加入2.4mL的1,1,3,3-四甲基二硅氧烷S2(0.76g/mL,134.33g/mol,13.54mmol),S1与S2物质的量比为5︰1,S1可以稍过量,氩气除氧三次。升温至55℃,再用微量进样器加入76.5μL三氟甲磺酸S3(1.696g/mL,150.08g/mol,0.86mmol)。55℃下反应72h。反应完毕后,冷却至室温,将产物溶于200ml乙醚,在分液漏斗中用去离子水多次萃取体系中的三氟甲磺酸。加入无水硫酸镁搅拌约1h除去水分,过滤。旋蒸除去乙醚。在120℃真空干燥约8h,得到硅氢键封端的PDMS预聚物S4-3(19.7g,收率90%)。其结构及其聚合度由核磁氢谱积分确定为20。Step 1, synthesis of prepolymer S4-3: add 21 mL S1 (0.956 g/mL, 296.62 g/mol, 67.68 mmol) to the schlenk bottle with a pipette under nitrogen protection, seal the top with a rubber stopper, and then add 2.4 mL 1,1,3,3-tetramethyldisiloxane S2 (0.76 g/mL, 134.33 g/mol, 13.54 mmol) with a syringe. The molar ratio of S1 to S2 is 5:1. S1 can be slightly excessive, and argon gas is used for deoxygenation three times. Heat to 55°C, and then add 76.5 μL trifluoromethanesulfonic acid S3 (1.696 g/mL, 150.08 g/mol, 0.86 mmol) with a microinjector. React at 55°C for 72 hours. After the reaction is completed, cool to room temperature, dissolve the product in 200 ml of ether, and extract the trifluoromethanesulfonic acid in the system with deionized water in a separatory funnel several times. Add anhydrous magnesium sulfate and stir for about 1 hour to remove moisture, and filter. Remove the ether by rotary evaporation. Dry under vacuum at 120°C for about 8 hours to obtain a silicon-hydrogen bond-terminated PDMS prepolymer S4-3 (19.7 g, yield 90%). Its structure and degree of polymerization were determined to be 20 by nuclear magnetic hydrogen spectrum integration.
1H NMR(500MHz,CDCl3)δ4.72-4.69(m,2H),0.19-0.07(m,131.24H);2/131.24=2/(6n+12),n=20,Mn=1628g/mol.
1 H NMR (500 MHz, CDCl3) δ 4.72-4.69 (m, 2H), 0.19-0.07 (m, 131.24H); 2/131.24 = 2/(6n+12), n = 20, Mn = 1628 g/mol.
GPC(DMF):PDI 1.181.GPC(DMF):PDI 1.181.
步骤2合成预聚物Z8-9-1:在氮气气氛中将干燥的乙烯基化合物S5-1(7.6g,152.62g/mol,50mmol))与反应原料S7-3(15.0g,150.2g/mol,100mmol)混合溶于干燥1,4-二氧六环(120mL)中。 加入固体氢氧化钾(5.6g,56.10g/mol,100mmol),50℃下反应48h。核磁氢谱确定反应完成。待反应完全后,将混合物冷却至室温,减压除去溶剂后,硅胶柱层析(正己烷/乙酸乙酯=1/1)得到预聚物Z8-9-1(7.9g,产率57%)。Step 2 Synthesis of prepolymer Z8-9-1: In a nitrogen atmosphere, the dried vinyl compound S5-1 (7.6 g, 152.62 g/mol, 50 mmol)) and the reaction raw material S7-3 (15.0 g, 150.2 g/mol, 100 mmol) were mixed and dissolved in dry 1,4-dioxane (120 mL). Solid potassium hydroxide (5.6 g, 56.10 g/mol, 100 mmol) was added and reacted at 50°C for 48 h. The nuclear magnetic hydrogen spectrum confirmed that the reaction was complete. After the reaction was complete, the mixture was cooled to room temperature, the solvent was removed under reduced pressure, and silica gel column chromatography (n-hexane/ethyl acetate = 1/1) was used to obtain prepolymer Z8-9-1 (7.9 g, yield 57%).
1H NMR(500MHz,CDCl3)δ7.38(d,J=10.0Hz,2H),7.30(d,J=10.0Hz,2H),6.70(dd,J=15&10Hz,1H),5.73(d,J=20.0Hz,1H),5.23(d,J=15Hz),4.54(s,2H),3.80-3.55(m,12H)。
1 H NMR (500 MHz, CDCl3) δ 7.38 (d, J = 10.0 Hz, 2H), 7.30 (d, J = 10.0 Hz, 2H), 6.70 (dd, J = 15&10 Hz, 1H), 5.73 (d, J = 20.0 Hz, 1H), 5.23 (d, J = 15 Hz), 4.54 (s, 2H), 3.80-3.55 (m, 12H).
步骤3合成预聚物Z8-5-3:在氮气气氛中将干燥的乙烯基化合物Z8-9-1(7.9g,270g/mol,29.2mmol))与反应原料S11三乙胺(3.5g,101.2g/mol,35.0mmol),混合溶于干燥二氯甲烷(120mL)中,并在冰浴下冷却搅拌15分钟。分3次加入反应原料S10对甲苯磺酰氯(5.4g,154.6g/mol,35.0mmol)。恢复至25℃搅拌24小时。待反应完全,减压过滤除去盐,滤液减压除去溶剂后,硅胶柱层析(正己烷/乙酸乙酯=3/1)得到预聚物Z8-5-3(6.4g,产率52.4%。Step 3: Synthesis of prepolymer Z8-5-3: In a nitrogen atmosphere, the dried vinyl compound Z8-9-1 (7.9 g, 270 g/mol, 29.2 mmol)) and the reaction raw material S11 triethylamine (3.5 g, 101.2 g/mol, 35.0 mmol) were mixed and dissolved in dry dichloromethane (120 mL), and cooled and stirred in an ice bath for 15 minutes. The reaction raw material S10 p-toluenesulfonyl chloride (5.4 g, 154.6 g/mol, 35.0 mmol) was added in 3 portions. The temperature was restored to 25 ° C and stirred for 24 hours. After the reaction was complete, the salt was removed by filtration under reduced pressure, and the filtrate was decompressed to remove the solvent, and the prepolymer Z8-5-3 (6.4 g, yield 52.4%) was obtained by silica gel column chromatography (n-hexane/ethyl acetate = 3/1).
1H NMR(500MHz,CDCl3)δ7.75(d,J=10.0Hz,2H),7.40-7.20(m,6H),6.66(dd,J=15&5Hz,1H),5.70(d,J=25Hz,1H),5.25-5.18(m,1H),4.50(s,2H),4.20-4.00(m,2H),3.70-3.50(m,10H),2.38(s,3H).Mn=420.5g/mol
1 H NMR (500 MHz, CDCl3) δ7.75 (d, J = 10.0 Hz, 2H), 7.40-7.20 (m, 6H), 6.66 (dd, J = 15 & 5 Hz, 1H), 5.70 (d, J = 25 Hz, 1H), 5.25-5.18 (m, 1H), 4.50 (s, 2H), 4.20-4.00 (m, 2H), 3.70-3.50 (m, 10H), 2.38 (s, 3H). Mn = 420.5 g/mol
步骤4,合成预聚物Z8-5:在氩气中将干燥的乙烯基化合物Z8-5-3(5.3g,420.5g/mol,12.5mmol)与反应原料Z6-1(1.1g,85.1g/mol,12.5mmol)混合溶于干燥乙腈(120mL)中。80℃下反应24h。核磁氢谱确定反应完成。待反应完全后,将混合物冷却至室温,然后将5ml 0.5M含有氢氧化钾S7-1(0.48g)的甲醇溶液加入到混合物中终止反应,并搅拌3小时。减压除去溶剂后,将产物溶于100ml二氯甲烷,过滤除去残留无机盐及过量氢氧化钾。减压除去溶剂,并将所得聚合物在真空下干燥,得到乙烯基封端的PMOXA预聚物Z8-5(3.9g,收率89%)。其结构及其聚合度由核磁氢谱积分确定。Step 4, synthesis of prepolymer Z8-5: dry vinyl compound Z8-5-3 (5.3 g, 420.5 g/mol, 12.5 mmol) and reaction raw material Z6-1 (1.1 g, 85.1 g/mol, 12.5 mmol) were mixed and dissolved in dry acetonitrile (120 mL) in argon. React at 80 ° C for 24 h. The reaction was completed by nuclear magnetic hydrogen spectrum. After the reaction was complete, the mixture was cooled to room temperature, and then 5 ml of 0.5 M methanol solution containing potassium hydroxide S7-1 (0.48 g) was added to the mixture to terminate the reaction, and stirred for 3 hours. After removing the solvent under reduced pressure, the product was dissolved in 100 ml of dichloromethane, and the residual inorganic salts and excess potassium hydroxide were filtered out. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain a vinyl-terminated PMOXA prepolymer Z8-5 (3.9 g, yield 89%). Its structure and degree of polymerization were determined by nuclear magnetic hydrogen spectrum integration.
1H NMR(500MHz,CDCl3)δ7.86-7.70(m,1.49H),7.45-7.28(m,4.72H),6.80-6.65(m,1H),5.77-5.72(m,1H),5.30-5.23(m,1H),4.54(s,2H),4.17-4.15(m,1.85H),3.70-3.40(m,15.71H),2.20-1.95(m,4.12H),1/3m=1/4.12,m=1.4.Mn=385g/mol
1 H NMR (500MHz,CDCl3)δ7.86-7.70(m,1.49H),7.45-7.28(m,4.72H),6.80-6.65(m,1H),5.77-5.72(m,1H),5.30-5.23(m,1H),4.54(s,2H),4.17-4.15(m,1.85H),3.70-3.40(m,15.71H),2.20-1.95(m,4.12H),1/3m=1/4.12,m=1.4.Mn=385g/mol
GPC(DMF):PDI 1.197.GPC(DMF):PDI 1.197.
步骤5,三嵌段P5合成:在氩气中将反应原料S4-3(1.6g,1628g/mol,1mmol)与干燥的反应原料Z8-5(0.96g,385g/mol,2.5mmol)溶于20ml干燥的甲苯/乙腈混合溶剂(1/1)中,室温下待原料充分溶解后,加入120uL Karstedt催化剂(in xylene,Pt~2%),升温至80℃,80℃下搅拌48h,待反应完全后,将混合物冷却至室温,过滤,固体用乙醚(10mL)洗三次后,将产物溶于100ml乙醇中,并用超过600ml的乙醇通过再生纤维素膜(Millipore,截留分子量为1K)渗滤纯化。减压除去溶剂,并将所得聚合物在真空下干燥,得到五嵌段PMOXA-PEG-PDMS-PEG-PMOXA(1.3-3-20-3-1.3)聚合物P5(1.0g,收率42%)。Step 5, synthesis of triblock P5: In argon, the reaction raw material S4-3 (1.6 g, 1628 g/mol, 1 mmol) and the dry reaction raw material Z8-5 (0.96 g, 385 g/mol, 2.5 mmol) were dissolved in 20 ml of dry toluene/acetonitrile mixed solvent (1/1). After the raw materials were fully dissolved at room temperature, 120 uL of Karstedt catalyst (in xylene, Pt~2%) was added, the temperature was raised to 80°C, and stirred at 80°C for 48 h. After the reaction was complete, the mixture was cooled to room temperature and filtered. The solid was washed three times with ether (10 mL), and the product was dissolved in 100 ml of ethanol and purified by filtration through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 1K) with more than 600 ml of ethanol. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain pentablock PMOXA-PEG-PDMS-PEG-PMOXA (1.3-3-20-3-1.3) polymer P5 (1.0 g, yield 42%).
1H NMR(500MHz,CDCl3)δ7.80-7.77(m,1H),7.40-7.10(m,3.9H),4.54-4.49(m,1.28H),4.20- 4.10(m,1.00H),3.75-3.50(m,8.19H),2.70-2.50(m,0.99H),2.35-1.90(m,1.98H),0.90-0.82(m,0.82H),0.07-0.00(m,65.47H).1.98/65.47=3m/132,m=1.34,Mn=2398g/mol;
1 H NMR (500 MHz, CDCl3) δ 7.80-7.77 (m, 1H), 7.40-7.10 (m, 3.9H), 4.54-4.49 (m, 1.28H), 4.20- 4.10 (m, 1.00H), 3.75-3.50 (m, 8.19H), 2.70-2.50 (m, 0.99H), 2.35-1.90 (m, 1.98H), 0.90-0.82 (m, 0.82H), 0.07-0.00 (m, 65.47H). 1.98/65.47=3m/132, m=1.34, Mn=2398g/mol;
GPC(DMF):PDI 1.230.GPC(DMF):PDI 1.230.
实施例6三嵌段聚合物P5的液滴微流体制备与测试Example 6 Preparation and testing of droplet microfluidics of triblock polymer P5
根据液滴微流控参考文献:According to the droplet microfluidics reference:
1)Janelle R.Anderson et al.Fabrication of Topologically Complex Three-Dimensional Microfluidic Systems in PDMS by Rapid Prototyping.Anal.Chem.2000,72,3158-3164;1) Janelle R. Anderson et al. Fabrication of Topologically Complex Three-Dimensional Microfluidic Systems in PDMS by Rapid Prototyping. Anal. Chem. 2000, 72, 3158-3164;
2)George M.Whitesides.The origins and the future of microfluidics.Nature,2006,442,368-373.2) George M. Whitesides. The origins and the future of microfluidics. Nature, 2006, 442, 368-373.
测得本申请聚合物P5的液滴可以稳定存在30分钟以上,均一性良好,且液滴间无明显融合。It was measured that the droplets of the polymer P5 of the present application can exist stably for more than 30 minutes, have good uniformity, and there is no obvious fusion between the droplets.
Claims (12)
- 一种式V所示聚合物:A polymer represented by formula V:其中,in,所述R为-OR t1、-NR t2R t3、-COOMe、-(CH 2) n1SH、被1、2或3个氧代基取代的5-10元杂芳基、-O(CH 2) n2OH、-OP(O)(OMe)、-OP(O)(OMe)(O(CH 2) n3N +(Et) 3, The R is -ORt1 , -NRt2Rt3 , -COOMe , -( CH2 ) n1SH , a 5-10 membered heteroaryl substituted by 1, 2 or 3 oxo groups, -O( CH2 ) n2OH , -OP(O)(OMe), -OP(O)(OMe)(O( CH2 ) n3N + (Et) 3 ,所述R t1、R t2、R t3独立地为H、Ts、C 1-C 6烷基或-(CH 2) n4SH; Said R t1 , R t2 , and R t3 are independently H, Ts, C 1 -C 6 alkyl or -(CH 2 ) n4 SH;n1、n3和n4独立地为0、1、2、3、4、5或6;n1, n3 and n4 are independently 0, 1, 2, 3, 4, 5 or 6;n2为2、3、4、5、6、7、8或9;n2 is 2, 3, 4, 5, 6, 7, 8 or 9;所述 中,所述R c为氢、C 1-C 6烷基、C 1-C 6烷氧基、-CN或-NO 2; Said wherein R c is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, -CN or -NO 2 ;所述 中,所述R a为(CH 2) n,n为3、4或5,所述R b为氢、C 1-C 6烷基或乙酰基; Said wherein said Ra is ( CH2 ) n , n is 3, 4 or 5, and said Rb is hydrogen, C1 - C6 alkyl or acetyl;所述 为聚2-甲基恶唑啉、聚磷脂、聚乙二醇、聚乙烯醇、聚乙烯吡咯烷酮、聚丙烯酰胺、聚甲基丙烯酸甲酯、聚(N,N-二甲基丙烯酰胺)、聚酰基亚烷基亚胺、聚羟基烷基丙烯酸酯、聚2-甲基恶唑啉聚乙二醇或聚2-甲基恶唑啉聚磷脂; Said It is poly-2-methyloxazoline, polyphospholipid, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polymethyl methacrylate, poly(N,N-dimethylacrylamide), polyacylalkylene imine, polyhydroxyalkyl acrylate, poly-2-methyloxazoline polyethylene glycol or poly-2-methyloxazoline polyphospholipid;所述R 1为C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 6-C 12芳基、-(CH 2) nOH、 或-(CH 2) n-CH=CH 2,其中,n为3、4或5; The R 1 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 12 aryl, -(CH 2 ) n OH, or -(CH 2 ) n -CH=CH 2 , wherein n is 3, 4 or 5;所述R 1’为C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 6-C 12芳基、-(CH 2) nOH、 或-(CH 2) n-CH=CH 2,其中,n为3、4或5; The R 1' is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 12 aryl, -(CH 2 ) n OH, or -(CH 2 ) n -CH=CH 2 , wherein n is 3, 4 or 5;所述Y为C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 6-C 12芳基、-(CH 2) nOH、 或-(CH 2) n-CH=CH 2,其中,n为3、4或5; The Y is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 6 -C 12 aryl, -(CH 2 ) n OH, or -(CH 2 ) n -CH=CH 2 , wherein n is 3, 4 or 5;所述p为20-50;The p is 20-50;所述的5-10元杂芳基中,杂原子的数量独立地为1个、2个或3个,所述杂原子独立地选自N、O和S中的一种或多种。In the 5-10 membered heteroaryl group, the number of heteroatoms is independently 1, 2 or 3, and the heteroatoms are independently selected from one or more of N, O and S.
- 如权利要求1所述的式V所示聚合物,其特征在于,所述式V所示聚合物满足下列条件中的一个或多个:The polymer represented by formula V according to claim 1, characterized in that the polymer represented by formula V satisfies one or more of the following conditions:a)所述R 1为C 1-C 6烷基;优选为甲基; a) R 1 is a C 1 -C 6 alkyl group, preferably a methyl group;b)所述R 1’为C 1-C 6烷基;优选为甲基; b) R 1' is a C 1 -C 6 alkyl group, preferably a methyl group;c)所述Y为C 1-C 6烷基;优选为甲基; c) Y is a C 1 -C 6 alkyl group, preferably a methyl group;e)所述p为20-47;优选为20或35。e) said p is 20-47; preferably 20 or 35.
- 如权利要求2所述的式V所示聚合物,其特征在于,所述式V所示聚合物满足下列条件中的一个或多个:The polymer represented by formula V according to claim 2, characterized in that the polymer represented by formula V satisfies one or more of the following conditions:a)所述 为 其中,每个R 2各自独立地为C 1-C 3烷基,优选为甲基;每个m各自独立地为1-22的任意数值;优选为1-6的任意数值;更优选1、1.1、1.3、3.6、3.8或5.4;进一步优选1、1.1、1.3或3.6;每个w各自独立地为1-22的任意数值;优选为1-6的任意数值;更优选为3; a) for wherein each R 2 is independently a C 1 -C 3 alkyl group, preferably a methyl group; each m is independently any value from 1 to 22; preferably any value from 1 to 6; more preferably 1, 1.1, 1.3, 3.6, 3.8 or 5.4; further preferably 1, 1.1, 1.3 or 3.6; each w is independently any value from 1 to 22; preferably any value from 1 to 6; more preferably 3;c)所述聚恶唑啉类聚合物优选为聚2-甲基恶唑啉。c) The polyoxazoline polymer is preferably poly-2-methyloxazoline.
- 一种如权利要求1-4任一项所述的式V所示聚合物的制备方法,其包括如下步骤:在溶剂中,在惰性气氛中,将式Z8所示聚合物和式S4所示聚合物在催化剂的作用下进行如下所示的加成反应,制得式V所示聚合物,即可,A method for preparing a polymer of formula V as claimed in any one of claims 1 to 4, comprising the following steps: in a solvent, in an inert atmosphere, subjecting a polymer of formula Z8 and a polymer of formula S4 to an addition reaction as shown below under the action of a catalyst to obtain a polymer of formula V, that is,其中,in,
- 如权利要求5所述的式V所示聚合物的制备方法,其特征在于,所述制备方法满足下列条件中的一个或多个:The method for preparing the polymer of formula V according to claim 5, characterized in that the preparation method satisfies one or more of the following conditions:a)所述催化剂为H 2PtCl 2或铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液;优选为铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷络合物溶液; a) The catalyst is H 2 PtCl 2 or a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution; preferably a platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex solution;b)所述溶剂为氯代烃类溶剂、醚类溶剂、酯类溶剂、芳烃类溶剂和腈类溶剂中的一种或多种;所述的氯代烃类溶剂优选氯仿和二氯乙烷一种或多种;所述的醚类溶剂优选四氢呋喃;所述的酯类溶剂优选乙酸乙酯;所述的芳烃类溶剂优选甲苯;所述的腈类溶剂优选苯甲腈和乙腈的一种或多种;所述溶剂更优选芳烃类溶剂和腈类溶剂的混合溶剂,进一步优选甲苯和乙腈混合溶剂;b) the solvent is one or more of a chlorinated hydrocarbon solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent and a nitrile solvent; the chlorinated hydrocarbon solvent is preferably one or more of chloroform and ethylene dichloride; the ether solvent is preferably tetrahydrofuran; the ester solvent is preferably ethyl acetate; the aromatic hydrocarbon solvent is preferably toluene; the nitrile solvent is preferably one or more of benzonitrile and acetonitrile; the solvent is more preferably a mixed solvent of an aromatic hydrocarbon solvent and a nitrile solvent, and further preferably a mixed solvent of toluene and acetonitrile;c)所述Z8与S4的摩尔比为2.5-3;优选2.5;c) the molar ratio of Z8 to S4 is 2.5-3; preferably 2.5;d)所述Z8与所述催化剂的摩尔体积比为15-30mol/L;d) the molar volume ratio of the Z8 to the catalyst is 15-30 mol/L;e)所述Z8与所述溶剂的摩尔体积比为0.05-0.2mol/L;优选为0.125mol/L;e) the molar volume ratio of the Z8 to the solvent is 0.05-0.2 mol/L; preferably 0.125 mol/L;f)所述反应的温度为60~80℃;优选60℃或80℃;f) the reaction temperature is 60-80°C; preferably 60°C or 80°C;g)所述反应的反应时间为24~48h;优选24h或48h;g) the reaction time of the reaction is 24 to 48 hours; preferably 24 hours or 48 hours;h)所述惰性气氛为氮气气氛或氩气气氛;h) the inert atmosphere is a nitrogen atmosphere or an argon atmosphere;i)所述反应包括后处理;所述的后处理步骤为使用乙醇和再生纤维素膜进行渗滤纯化;优选使用截留分子量为1K的再生纤维素膜进行渗滤纯化;i) the reaction includes post-treatment; the post-treatment step is to use ethanol and regenerated cellulose membrane for diafiltration purification; preferably, a regenerated cellulose membrane with a molecular weight cut-off of 1K is used for diafiltration purification;j)所述反应的加料顺序为先将Z8溶于溶剂,后加入S4,再加入催化剂;所述反应的加料顺序优选先将Z8溶于溶剂,待其完全溶解或大部分溶解后,加入S4,待其完全溶解后,再加入催化剂。j) The order of adding materials for the reaction is to first dissolve Z8 in the solvent, then add S4, and then add the catalyst; the order of adding materials for the reaction is preferably to first dissolve Z8 in the solvent, add S4 after it is completely dissolved or mostly dissolved, and then add the catalyst after it is completely dissolved.
- 如权利要求6所述的式V所示聚合物的制备方法,其特征在于,所述制备方法满足下列条件中的一个或多个:The method for preparing the polymer of formula V according to claim 6, characterized in that the preparation method satisfies one or more of the following conditions:a)当所述溶剂为芳烃类溶剂和腈类溶剂的混合溶剂时,在所述芳烃类溶剂和腈类溶剂的混合溶剂中,所述芳烃类溶剂和腈类溶剂的体积比为1:0.01-1:3;优选1:1;a) when the solvent is a mixed solvent of an aromatic hydrocarbon solvent and a nitrile solvent, in the mixed solvent of the aromatic hydrocarbon solvent and the nitrile solvent, the volume ratio of the aromatic hydrocarbon solvent to the nitrile solvent is 1:0.01-1:3; preferably 1:1;b)所述催化剂中铂含量为1-4%;优选2%;b) the platinum content of the catalyst is 1-4%, preferably 2%;c)当所述反应包括后处理时,所述后处理中,所述式Z8所示化合物与乙醇的摩尔体积比为1:40mol/L;c) when the reaction includes post-treatment, in the post-treatment, the molar volume ratio of the compound represented by formula Z8 to ethanol is 1:40 mol/L;d)所述反应具体操作为a)先将Z8溶于溶剂,充分搅拌至完全溶解或大部分溶解;b)加入S4,待其溶解,充分搅拌5分钟;c)加入催化剂,充分搅拌5-10分钟;d)升温搅拌。d) The specific operation of the reaction is as follows: a) first dissolve Z8 in a solvent and stir thoroughly until it is completely dissolved or mostly dissolved; b) add S4, wait for it to dissolve, and stir thoroughly for 5 minutes; c) add a catalyst and stir thoroughly for 5-10 minutes; d) heat and stir.
- 如权利要求5-7任一项所述的式V所示聚合物的制备方法,其特征在于,所述制备方法还包括式Z8所示聚合物的制备方法,其包括如下步骤:在溶剂中,在惰性气氛中,将式S5所示化合物、式Z6所示化合物和淬灭试剂S7进行如下所示的反应,制得式Z8所示聚合物,即可,The method for preparing a polymer of formula V according to any one of claims 5 to 7, characterized in that the preparation method further comprises a method for preparing a polymer of formula Z8, comprising the following steps: in a solvent, in an inert atmosphere, reacting a compound of formula S5, a compound of formula Z6 and a quenching reagent S7 as shown below to obtain a polymer of formula Z8, that is,所述X为卤素、OTf或OTs;Said X is halogen, OTf or OTs;所述淬灭试剂S7为无机碱(例如KOH)或RH,R定义如权利要求1-4任一项所述;The quenching reagent S7 is an inorganic base (such as KOH) or RH, and R is defined as described in any one of claims 1-4;
- 如权利要求8所述的式V所示聚合物的制备方法,其特征在于,其中式Z8所示聚合物的制备方法满足下列条件中的一个或多个:The method for preparing a polymer represented by formula V as claimed in claim 8, wherein the method for preparing a polymer represented by formula Z8 satisfies one or more of the following conditions:a)所述溶剂为腈类溶剂;优选乙腈;a) the solvent is a nitrile solvent; preferably acetonitrile;c)所述X为Br、Cl或OTs;c) X is Br, Cl or OTs;d)所述淬灭试剂S7为氢氧化钾的甲醇溶液、 优选氢氧化钾浓度为0.5M的甲醇溶液; d) the quenching reagent S7 is a methanol solution of potassium hydroxide, Preferably, the potassium hydroxide concentration is 0.5M methanol solution;e)所述式S5所示化合物与式Z6所示化合物的摩尔比为2:1-1:8;优选1:1或1:4;e) the molar ratio of the compound represented by formula S5 to the compound represented by formula Z6 is 2:1-1:8; preferably 1:1 or 1:4;f)所述式S5所示化合物与溶剂的摩尔体积比为1:1.5mol/L-1:3mol/L;优选50:120mol/L;f) the molar volume ratio of the compound represented by formula S5 to the solvent is 1:1.5 mol/L-1:3 mol/L; preferably 50:120 mol/L;g)所述反应温度为40-120℃;优选80℃;g) the reaction temperature is 40-120°C; preferably 80°C;h)所述反应时间为12-48小时;优选24小时;h) the reaction time is 12-48 hours; preferably 24 hours;i)所述惰性气氛为氮气气氛或氩气气氛;i) the inert atmosphere is a nitrogen atmosphere or an argon atmosphere;j)加入所述淬灭试剂S7的操作为在反应冷却至室温后加入;优选在反应冷却至室温后加入再搅拌3小时;j) adding the quenching reagent S7 after the reaction is cooled to room temperature; preferably, adding the quenching reagent S7 after the reaction is cooled to room temperature and stirring for 3 hours;k)所述反应包括后处理;所述的后处理步骤为使用乙醇和再生纤维素膜进行渗滤纯化;优选使用截留分子量为1K的再生纤维素膜进行渗滤纯化。k) The reaction includes post-treatment; the post-treatment step is to use ethanol and regenerated cellulose membrane for diafiltration purification; preferably, a regenerated cellulose membrane with a molecular weight cut-off of 1K is used for diafiltration purification.
- 如权利要求9所述的式V所示聚合物的制备方法,其特征在于,其中式Z8所示聚合物的制备方法满足下列条件中的一个或多个:The method for preparing a polymer represented by formula V according to claim 9, wherein the method for preparing a polymer represented by formula Z8 satisfies one or more of the following conditions:a)当所述淬灭试剂S7为氢氧化钾的甲醇溶液时,所述式S5所示化合物与淬灭试剂S7的摩尔体积比为5-20mol/L;优选10mol/L;a) when the quenching agent S7 is a methanol solution of potassium hydroxide, the molar volume ratio of the compound represented by formula S5 to the quenching agent S7 is 5-20 mol/L; preferably 10 mol/L;b)当所述淬灭试剂S7为 时,所述式S5所示化合物与淬灭试剂S7的摩尔比为1:2-2:1;优选1:1; b) When the quenching reagent S7 is When the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:2-2:1; preferably 1:1;c)当所述淬灭试剂S7为 时,所述式S5所示化合物与淬灭试剂S7的摩尔比为1:2-2:1;优选1:1; c) When the quenching reagent S7 is When the molar ratio of the compound represented by formula S5 to the quenching reagent S7 is 1:2-2:1; preferably 1:1;d)当所述反应包括后处理时,所述后处理中,所述式S5所示化合物与乙醇的摩尔体积比为5:70mol/L。d) When the reaction includes post-treatment, in the post-treatment, the molar volume ratio of the compound represented by formula S5 to ethanol is 5:70 mol/L.
- 一种如权利要求11所述的式Z8所示聚合物的制备方法,其包括如下步骤:在溶剂中,在惰性气氛中,将式S5所示化合物、式Z6所示化合物和淬灭试剂S7进行如下所示的反应,制得式Z8所示聚合物,即可,A method for preparing a polymer represented by formula Z8 as claimed in claim 11, comprising the following steps: in a solvent, in an inert atmosphere, reacting a compound represented by formula S5, a compound represented by formula Z6 and a quenching reagent S7 as shown below to obtain a polymer represented by formula Z8, that is,
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2022/141241 WO2024130673A1 (en) | 2022-12-23 | 2022-12-23 | Polymer and preparation method therefor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2022/141241 WO2024130673A1 (en) | 2022-12-23 | 2022-12-23 | Polymer and preparation method therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2024130673A1 true WO2024130673A1 (en) | 2024-06-27 |
Family
ID=91587431
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2022/141241 WO2024130673A1 (en) | 2022-12-23 | 2022-12-23 | Polymer and preparation method therefor |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2024130673A1 (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02182724A (en) * | 1989-01-10 | 1990-07-17 | Kao Corp | Poly(n-acylalkyleneimine)-based copolymer and use thereof |
US20080305149A1 (en) * | 2007-06-11 | 2008-12-11 | Thomas Hirt | Mucoadhesive vesicles for drug delivery |
CN102066986A (en) * | 2008-03-17 | 2011-05-18 | 博士伦公司 | Lenses comprising amphiphilic multiblock copolymers |
CN106232686A (en) * | 2014-03-26 | 2016-12-14 | 应用仿生学有限公司 | New polymers and the method manufacturing film |
CN106459410A (en) * | 2014-05-01 | 2017-02-22 | 博通分离膜技术(北京)有限公司 | A synthetic process of a block copolymer and uses thereof |
CN106687508A (en) * | 2014-07-23 | 2017-05-17 | 道康宁公司 | Silicone emulsions |
-
2022
- 2022-12-23 WO PCT/CN2022/141241 patent/WO2024130673A1/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02182724A (en) * | 1989-01-10 | 1990-07-17 | Kao Corp | Poly(n-acylalkyleneimine)-based copolymer and use thereof |
US20080305149A1 (en) * | 2007-06-11 | 2008-12-11 | Thomas Hirt | Mucoadhesive vesicles for drug delivery |
CN102066986A (en) * | 2008-03-17 | 2011-05-18 | 博士伦公司 | Lenses comprising amphiphilic multiblock copolymers |
CN106232686A (en) * | 2014-03-26 | 2016-12-14 | 应用仿生学有限公司 | New polymers and the method manufacturing film |
CN106459410A (en) * | 2014-05-01 | 2017-02-22 | 博通分离膜技术(北京)有限公司 | A synthetic process of a block copolymer and uses thereof |
CN106687508A (en) * | 2014-07-23 | 2017-05-17 | 道康宁公司 | Silicone emulsions |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Narain et al. | Synthesis and aqueous solution properties of novel sugar methacrylate-based homopolymers and block copolymers | |
Wurm et al. | Double-hydrophilic linear-hyperbranched block copolymers based on poly (ethylene oxide) and poly (glycerol) | |
Dai et al. | Synthesis, self‐assembly and recognition properties of biomimetic star‐shaped poly (ε‐caprolactone)‐b‐glycopolymer block copolymers | |
Zhang et al. | Influence of solvophilic homopolymers on RAFT polymerization-induced self-assembly | |
NO314589B1 (en) | Block polymer having functional groups at both ends, living block polymer, process for preparing the block polymer and polymeric cell | |
CN110003481B (en) | Preparation method of eight-arm hetero-arm star polymer | |
TW201602177A (en) | A novel synthetic process of a block copolymer and a novel use | |
JP2010511065A (en) | Brush copolymer | |
Huo et al. | Light/temperature dual-responsive ABC miktoarm star terpolymer micelles for controlled release | |
Garcia et al. | Water soluble triblock and pentablock poly (methacryloyl nucleosides) from copper-mediated living radical polymerisation using PEG macroinitiators | |
Kim et al. | Facile synthesis of amphiphilic bottlebrush block copolymers bearing pyridine pendants via click reaction from protected alkyne side groups | |
US8546488B2 (en) | Cleavable block copolymers, functionalized nanoporous thin films and related methods of preparation | |
JP4969166B2 (en) | Amphiphilic triblock copolymer composed of poly (2-vinylpyridine) block and poly (alkylisocyanate) block and polymerization method thereof | |
WO2024130673A1 (en) | Polymer and preparation method therefor | |
CN112961278A (en) | Functionalized vinyl pyrrolidone copolymer and preparation method thereof | |
WO2007026932A1 (en) | Random copolymer of oxazoline | |
WO2024130674A1 (en) | Method for preparing amphiphilic polymer | |
JP3807765B2 (en) | Block copolymer with polyacrylamide derivative and temperature-responsive polymer micelle | |
De Leon et al. | Fabrication of honeycomb films from highly functional dendritic structures: electrostatic force driven immobilization of biomolecules | |
Yamamoto et al. | Synthesis and PSA performance study for novel acrylic and butyl acrylate block copolymers | |
CN110305301B (en) | Amphiphilic dendritic sugar-containing copolymer and synthesis method thereof | |
JP2008280421A (en) | Hydrophilic film and method for producing the same | |
Chea et al. | Synthesis and self-assembly of cytidine-and guanosine-based copolymers | |
Hu et al. | Synthesis of styrene-norbornene diblock copolymers via ring-opening metathesis polymerization and nitroxide-mediated radical polymerization | |
JPH07101965A (en) | Alkoxysilane compound |