CN107880229B - Preparation method of end group modified polyacrylate block copolymer and polyacrylate block copolymer prepared by preparation method - Google Patents
Preparation method of end group modified polyacrylate block copolymer and polyacrylate block copolymer prepared by preparation method Download PDFInfo
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- CN107880229B CN107880229B CN201711295106.9A CN201711295106A CN107880229B CN 107880229 B CN107880229 B CN 107880229B CN 201711295106 A CN201711295106 A CN 201711295106A CN 107880229 B CN107880229 B CN 107880229B
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- Prior art keywords
- acrylate
- meth
- block copolymer
- polyacrylate block
- catalyst
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 57
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 64
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 27
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 18
- -1 alicyclic alcohols Chemical class 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 239000012038 nucleophile Substances 0.000 claims description 5
- 239000012434 nucleophilic reagent Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000012662 bulk polymerization Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- YJSRBMPTVVJSDP-UHFFFAOYSA-N 2-hydroxyethyl 2,3-dibromo-2-methylpropanoate Chemical compound BrCC(Br)(C)C(=O)OCCO YJSRBMPTVVJSDP-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims 2
- CRRUGYDDEMGVDY-UHFFFAOYSA-N 1-bromoethylbenzene Chemical compound CC(Br)C1=CC=CC=C1 CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 claims 1
- GTLWADFFABIGAE-UHFFFAOYSA-N 1-chloroethylbenzene Chemical compound CC(Cl)C1=CC=CC=C1 GTLWADFFABIGAE-UHFFFAOYSA-N 0.000 claims 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 20
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 14
- 125000005843 halogen group Chemical group 0.000 description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000010526 radical polymerization reaction Methods 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- 229910001428 transition metal ion Inorganic materials 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- ZPBJLEZUJMQIHC-UHFFFAOYSA-N 2-(2-bromo-2-methylpropanoyl)oxyethyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCCOC(=O)C(C)(C)Br ZPBJLEZUJMQIHC-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- AKKYWIOFTNMRRC-UHFFFAOYSA-N BrC(C(=O)OCCOC(C(CBr)(C)Br)=O)(C)C Chemical compound BrC(C(=O)OCCOC(C(CBr)(C)Br)=O)(C)C AKKYWIOFTNMRRC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229940120638 avastin Drugs 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DRIMNZQSBYUGBY-UHFFFAOYSA-N ethoxy-dimethoxy-prop-1-enylsilane Chemical compound CCO[Si](OC)(OC)C=CC DRIMNZQSBYUGBY-UHFFFAOYSA-N 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HLOLETUOZGAKMT-UHFFFAOYSA-N trimethoxysilyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)OC(=O)C(C)=C HLOLETUOZGAKMT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of polyacrylate block copolymer synthesis, and provides a preparation method of a terminal group modified polyacrylate block copolymer and a polyacrylate block copolymer prepared by the same; the preparation method comprises the following steps: (1) carrying out atom transfer radical polymerization (AGET ATRP) of an electron transfer generation catalyst on a polymerization system comprising an acrylate monomer, an initiator, a catalyst, a ligand and a reducing agent to prepare a polyacrylate block copolymer; (2) and carrying out in-situ end group modification on the polyacrylate block copolymer to prepare the end group modified polyacrylate block copolymer. The method removes the end halogen while functionalizing the polyacrylate block copolymer, and improves the product design and thermal stability.
Description
Technical Field
The invention belongs to the technical field of polyacrylate block copolymer synthesis, and particularly relates to a preparation method of a terminal group modified polyacrylate block copolymer and a polyacrylate block copolymer prepared by the same.
Background
The conventional preparation method of polyacrylate is free radical polymerization, including bulk polymerization, solution polymerization, emulsion polymerization and the like; the method is simple to operate and easy to produce, but has the defects of poor molecular design capability, uncontrollable molecular weight and molecular weight distribution of the polymer and the like.
In 1995, atom transfer radical polymerization was first proposed by the subject group of krzysztoff Matyjaszewski, which is a novel technique of controlled radical polymerization combining conventional radical polymerization and living/controlled radical polymerization. Compared with other living radical polymerization, the method has the advantages of wider applicable monomer range, stronger molecular design capability and mild polymerization conditions, can be used for preparing homopolymers and multi-block copolymers, and has wide prospect in the molecular design application of polymers. However, in industrial research, the common ATRP has been found to have some disadvantages not beneficial to industrialization, such as: the transition metal salt with low valence state is easy to be oxidized and lose efficacy, and needs to be preserved and reacted under the anaerobic condition; the residual metal ions after the reaction adversely affect the appearance and properties of the article.
In 2005, the Krzysztof Matyjaszewski group again proposed an active/controlled radical polymerization method that combines the advantages of conventional ATRP and reverse ATRP, i.e., atom transfer radical polymerization (AGET ATRP) that generates a catalyst by electron transfer. The method can directly use the transition metal with high valence as a catalyst, and simultaneously introduce a reducing substance to reduce the metal with high valence into low valence in situ so as to catalyze polymerization reaction, so that the polymerization reaction can be carried out without the operation of removing oxygen and in the presence of air or trace oxygen, thereby leading the operation process to be simpler. Meanwhile, the transition metal ions with high valence are reduced to low valence in situ, and the catalytic activity is higher; the oxidized high-valence metal can be reduced for reuse again, so that the use amount of the transition metal catalyst is greatly reduced; provides convenience for removing subsequent transition metal ions and greatly improves the possibility of industrialization of ATRP.
It is well known to those skilled in the art that AGET ATRP polymers contain halogens at the ends, which adversely affect the thermal stability of the polymer. Therefore, removal of such polymer terminal halogens is attracting attention. Known methods for removing the terminal halogen of ATRP polymerization products are: the removal of the terminal halogen is achieved by a click reaction using the terminal halogen as the raw material of the azide (macromol. Rapid Commun,18,1057-66,1997), which cannot achieve complete reaction, is highly toxicologically hazardous and is costly. Excess ligand is added, and the ligand is used as a chain transfer agent to remove the end halogen (Macromolecules,2005,38,271-279), and the method introduces a large amount of ligand into the system, improves the complexing capability with metal ions, but increases the difficulty of removing the metal catalyst. Patent document CN101484479A discloses a method for removing terminal halogen of ATRP polymerization product by adding thiol compound, but does not mention substitution of other nucleophiles, and introduction of excessive sulfur element has influence on color and odor of final product, and further removal of sulfur element is required, increasing process difficulty.
The polyacrylate has the characteristics of high bonding strength, oil resistance, weather resistance, strong ultraviolet resistance and the like, and is widely applied to the fields of paint, adhesive and sealant. However, the polyacrylate has a straight-chain structure, lacks crosslinking points, and has poor high and low temperature resistance and solvent resistance; therefore, effective block structure design is carried out, and functional groups are introduced into the terminal groups to modify polyacrylate, which becomes necessary for expanding application.
Disclosure of Invention
The invention aims to provide a preparation method of a terminal group modified polyacrylate block copolymer and the prepared polyacrylate block copolymer aiming at the problems of the polyacrylate block copolymer synthesized by the prior art, wherein the method removes terminal halogen while functionalizing the polyacrylate block copolymer, and improves product design and thermal stability.
In order to achieve the above object, the present invention provides a method for preparing a terminal-modified polyacrylate block copolymer, comprising the steps of:
(1) carrying out atom transfer radical polymerization (AGET ATRP) of an electron transfer generation catalyst on a polymerization system comprising an acrylate monomer, an initiator, a catalyst, a ligand and a reducing agent to prepare a polyacrylate block copolymer;
(2) and carrying out in-situ end group modification on the polyacrylate block copolymer to prepare the end group modified polyacrylate block copolymer.
According to the preparation method provided by the invention, preferably, in the step (2), the in-situ end group modification comprises the following steps: and after or during the atom transfer radical polymerization reaction of the electron transfer generation catalyst, contacting the polyacrylate block copolymer with a nucleophilic reagent to perform nucleophilic substitution reaction.
In the preparation method of the invention, the polyacrylate block copolymer obtained in the step (1) contains terminal halogen. Preferably, the molar ratio of terminal halogen to nucleophile in the polyacrylate block copolymer is 1: 1-2, more preferably 1: 1.1-1.3.
Preferably, the reaction conditions of the nucleophilic substitution reaction are: the reaction temperature is 70-90 ℃, and the reaction time is 0.5-1 h.
Preferably, the nucleophilic reagent is a compound which can generate nucleophilic substitution with end halogen in the polyacrylate block copolymer and contains a functional group, and the general formula is X-R1-Y,
wherein X is an electron donor capable of nucleophilic substitution selected from the group consisting of HO-, RO-, RCOO-, H2N-, HS-, CN-, or RC ≡ C-;
r1 is selected from C1-C40 alkyl, more preferably C2-C10 alkyl;
y is a functional group with reactivity and is selected from-OH, -COOH, -COOR, -SiR1x(OR2)3-x、-CHyF3-yor-CN; wherein x is 0, 1 or 2; y is 0, 1 or 2; r2 is selected from C1-C40 alkyl, preferably C1-C4 alkyl.
More preferably, the nucleophile is selected from silane compounds containing hydroxyl, amino or mercapto groups, and even more preferably from one or more of gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane and 3-amino-1-propanol.
According to the preparation method provided by the present invention, preferably, the acrylate monomer is selected from one or more of (meth) acrylate of linear alcohol, (meth) acrylate of branched alcohol and (meth) acrylate of alicyclic alcohol; preferably one or more selected from the group consisting of C4-C15 (meth) acrylates.
Preferably, the acrylate monomer is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, one or more of octadecyl (meth) acrylate, lauryl (meth) acrylate, 1, 2-ethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate; more preferably one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate and n-butyl (meth) acrylate.
The initiator is selected from one or more of alkyl halides, benzyl halides and alpha-halogenated esters, preferably from one or more of alpha-chlorobenzene ethane, alpha-bromobenzene ethane, ethyl alpha-bromoisobutyrate and ethylene glycol dibromoisobutyrate.
The catalyst is selected from transition metal halides. Preferably, the transition metal in the transition metal halide is selected from one or more of copper, iron, nickel, chromium, manganese, cobalt and ruthenium.
In a preferred embodiment of the invention, the transition metal halide is selected from one or more of copper chloride, copper bromide and ferric chloride.
The ligand is a compound containing nitrogen, oxygen, sulfur or phosphorus and capable of generating one or more coordination bonds with the transition metal to form a metal-ligand complex, preferably one or more selected from bipyridine, triphenylphosphine and N, N, N' -Pentamethyldiethylenetriamine (PMDETA).
The reducing agent is selected from one or more of hydroxylamines, alcohols, stannous octoate, ascorbic acid, reducing sugar, copper powder and iron powder, and is more preferably selected from one or more of ethylene glycol, stannous octoate and ascorbic acid. In a preferred embodiment of the invention, the reducing agent is ethylene glycol.
According to the preparation method provided by the invention, when the reducing agent used in the polymerization system in the step (1) is ethylene glycol, an acid-binding agent is required to be added for adjustment. The glycol is used as a reducing agent and is oxidized to generate oxalic acid, and the oxalic acid can be neutralized by adding an alkaline acid-binding agent to promote the forward redox reaction of the glycol. In a preferred embodiment of the present invention, the polymerization system in step (1) further comprises an acid-binding agent.
Preferably, the acid-binding agent is selected from one or more of sodium hydroxide, sodium bicarbonate and triethylamine, more preferably from sodium bicarbonate and/or triethylamine.
Preferably, the acrylate monomer: initiator: the molar ratio of the catalyst is 1000-10: 1: 0.1-1, more preferably 500-100: 1: 0.1-0.5; the catalyst comprises the following components: ligand: reducing agent: the molar ratio of the acid-applying agent is 1: 1-2: 1-5: 1-5, more preferably 1: 1-1.2: 1.5-2: 1.5-2.
According to the amount of the initiator, a catalyst, a ligand, a reducing agent and an acid-binding agent for promoting an oxidation-reduction reaction to improve the catalytic rate are added in proper proportion.
According to the preparation method provided by the invention, preferably, the atom transfer radical polymerization (AGET ATRP) of the electron transfer generation catalyst adopts bulk polymerization or solution polymerization. In a solution polymerization reaction system, the concentration of the catalyst is 5-2000 ppm, preferably 10-30 ppm.
Preferably, the solvent in the solution polymerization is selected from one or more of toluene, xylene, tetrahydrofuran, dichloromethane, N-dimethylamide, cyclohexanone, anisole and dioxane, preferably from one or more of toluene, tetrahydrofuran, cyclohexanone and anisole.
Preferably, the reaction temperature of the atom transfer radical polymerization reaction of the electron transfer generation catalyst is 25-150 ℃, and more preferably 50-90 ℃; the reaction time is 2-48h, more preferably 6-24 h.
It is another object of the present invention to provide a terminal-modified polyacrylate block copolymer prepared by the above-mentioned preparation method.
The invention also provides the polyacrylate block copolymer prepared by the preparation method, wherein the number average molecular weight of the polyacrylate block copolymer is 500-100000g/mol, preferably 5000-30000 g/mol; the molecular weight distribution is 1 to 1.6, preferably 1.1 to 1.3.
The polyacrylate main chain can be designed into a block copolymer of various acrylates by the preparation method, preferably a 2-4 block copolymer, and finally the polyacrylate block copolymer with a specific molecular structure, a specific molecular weight and extremely narrow molecular weight distribution is obtained.
According to the invention, an advanced AGET ATRP polymerization technology is adopted to prepare a polyacrylate block copolymer with a specific molecular structure, and then a nucleophilic substitution reaction is carried out on a nucleophilic reagent containing a functional group and terminal halogen of an AGET ATRP polymerization product when the polyacrylate block copolymer is modified, so that chain end functionality with controllable quantity can be designed; in addition, the halogen at the end of the polymer is removed while the functionalization is carried out, and finally the end group modified polyacrylate copolymer is obtained.
The technical scheme of the invention has the following beneficial effects:
(1) the invention adopts AGET ATRP controllable polymerization to carry out specific molecular structure design on the main chain structure of polyacrylate, the molecular weight is controllable, the molecular weight distribution is extremely narrow, and the product design and stability are greatly improved; compared with the traditional ATRP polymerization technology, the adopted AGET ATRP controllable polymerization technology has the advantages of milder reaction conditions, simpler post-treatment and easier realization of industrialization;
(2) the polyacrylate segmented copolymer prepared by adopting AGET ATRP technology is subjected to in-situ end group modification, so that the design of modified functionality is easier to perform; the AGET ATRP polymer product is functionalized, and simultaneously, the terminal halogen is removed, so that the thermal stability of the polymer is improved.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Firstly, the source of raw materials
Methyl Methacrylate (MMA), 99%, national pharmaceutical group chemical agents limited;
n-Butyl Acrylate (BA), 99%, chemical reagents of the national drug group, Inc.;
ethylene glycol dibromoisobutyrate (2-bromoisobutyrate), avastin reagent (shanghai) ltd;
triphenylphosphine (PPh)3) Aladdin reagent (Shanghai)) A limited company;
n, N, N', N "-Pentamethyldiethylenetriamine (PMDETA), Allantin reagent (Shanghai) Co., Ltd;
ferric chloride hexahydrate (FeCl)3˙6H2O), alatin reagent (shanghai) ltd;
cupric chloride (CuCl)2) Aladdin reagent (Shanghai) Inc.;
ethylene Glycol (EG), national drug group chemical agents ltd;
sodium bicarbonate (NaHCO)3) Aladdin reagent (Shanghai) Inc.;
gamma-aminopropyltrimethoxysilane, mayform advanced materials group ltd;
gamma-mercaptopropyltrimethoxysilane, mai ji gao new materials group ltd;
basic alumina, alatin reagent (shanghai) ltd;
3-amino-1-propanol, Toshiai (Shanghai) chemical industry development Co., Ltd.
Second, testing method
1. GPC measurement: shimadzu LC-20AD gel chromatograph GPC, refractive index detector, column temperature 30 deg.C, mobile phase is tetrahydrofuran (1mL/min), and polystyrene is used as standard sample.
2. Nuclear magnetic analysis: bruker AVANCE III 400M NMR spectrometer, deuterated chloroform as solvent.
The first embodiment is as follows:
firstly, two acrylate monomers of Methyl Methacrylate (MMA) and n-Butyl Acrylate (BA) are pretreated, and an aluminum peroxide column is used for removing a polymerization inhibitor. According to a molar ratio n (BA): n (Ethylene bis (2-Bromoisobutyrate)): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 50: 1: 1.2: 1: 1.5: 3, sequentially adding all reactants into a 100mL single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at 80 ℃ for 6h, rapidly introducing air, and cooling to terminate the reaction to obtain a Br-PBA-Br double-end macroinitiator; Br-PBA-Br as initiator, likewise in a molar ratio n (MMA): n (Br-PBA-Br): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 100: 1: 1.5: 1: 1: 1, synthesizing Br-PMMA-b-PBA-b-PMMA-Br according to the steps; adding gamma-aminopropyl trimethoxy silane when the polymerization reaction is ended, wherein the adding amount of the silane is n (Br-PBA-Br): n- (γ -aminopropyltrimethoxysilane) ═ 1: 2.2, continuing to react for 0.5 h; the polymerization product obtained by the reaction was subjected to an alumina column to remove transition metal ions, and subjected to GPC measurement. Wherein the number average molecular weight of Br-PBA-Br is 6800 (design value 6400), the molecular weight distribution is 1.18, the number average molecular weight of Br-PMMA-b-PBA-b-PMMA-Br is 17200 (design value 16400), and the molecular weight distribution is 1.20; the final resulting terminal siloxane-modified polyacrylate had 95% of the terminal halogen replaced by siloxane by nuclear magnetic analysis.
Example two:
firstly, two acrylate monomers of MMA and BA are pretreated, and an aluminum peroxide column is used for removing a polymerization inhibitor. According to a molar ratio n (BA): n (Ethylene bis (2-Bromoisobutyrate)): n (pmdeta): n (CuCl)2)：n(EG)：n(NaHCO3) 100: 1: 1.2: 1: 1.5: 3, sequentially adding all reactants into a 100mL single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at 90 ℃ for 6h, rapidly introducing air, and cooling to terminate the reaction to obtain a Br-PBA-Br double-end macroinitiator; taking Br-PBA-Br as an initiator, and similarly, adding the components in a certain molar ratio n (MMA): n (Br-PBA-Br): n (pmdeta): n (CuCl)2)：n(EG)：n(NaHCO3) 100: 1: 1.5: 1: 1: 1, synthesizing Br-PMMA-b-PBA-b-PMMA-Br according to the steps; adding gamma-mercaptopropyltrimethoxysilane when the polymerization reaction is ended, wherein the addition amount of the gamma-mercaptopropyltrimethoxysilane is n (Br-PBA-Br): n- (γ -mercaptopropyltrimethoxysilane) ═ 1: 2.6, continuing to react for 0.5 h; the polymerization product obtained by the reaction was subjected to an alumina column to remove transition metal ions, and subjected to GPC measurement. Wherein the number average molecular weight of Br-PBA-Br is 13500 (design value 12800), the molecular weight distribution is 1.23, the number average molecular weight of Br-PMMA-b-PBA-b-PMMA-Br is 24300 (design value 22800), and the molecular weight distribution is 1.20; the final resulting terminal siloxane-modified polyacrylate had 92% of the terminal halogen replaced by siloxane by nuclear magnetic analysis.
Example three:
firstly, two acrylate monomers of MMA and BA are pretreated, and an aluminum peroxide column is used for removing a polymerization inhibitor. According to a molar ratio n (BA): n (Ethylene bis (2-Bromoisobutyrate)): n (pmdeta): n (CuCl)2)：n(EG)：n(NaHCO3) 200: 1: 1.2: 1: 1.5: 3, sequentially adding all reactants into a 100mL single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at 90 ℃ for 6h, rapidly introducing air, and cooling to terminate the reaction to obtain a Br-PBA-Br double-end macroinitiator; Br-PBA-Br as initiator, likewise in a molar ratio n (MMA): n (Br-PBA-Br): n (pmdeta): n (CuCl)2)：n(EG)：n(NaHCO3) 100: 1: 1.5: 1: 1: 1, synthesizing Br-PMMA-b-PBA-b-PMMA-Br according to the steps; adding 3-amino-1-propanol when the polymerization reaction is terminated, wherein the adding amount is n (Br-PBA-Br): n (3-amino-1-propanol) ═ 1: 2.2, continuing to react for 0.5 h; the polymerization product obtained by the reaction was subjected to an alumina column to remove transition metal ions, and subjected to GPC measurement. Wherein the number average molecular weight of Br-PBA-Br is 27800 (design value 25600), the molecular weight distribution is 1.16, the number average molecular weight of Br-PMMA-b-PBA-b-PMMA-Br is 38600 (design value 35600), and the molecular weight distribution is 1.19; the final terminal fluoroalkyl-modified polyacrylate obtained was analyzed by nuclear magnetic analysis to have 92% of the terminal halogen replaced by hydroxyl.
Comparative example one:
firstly, two acrylate monomers of Methyl Methacrylate (MMA) and n-Butyl Acrylate (BA) are pretreated, and an aluminum peroxide column is used for removing a polymerization inhibitor. Xylene is used as a solvent, Azobisisobutyronitrile (AIBN) is used as an initiator, and the molar ratio of n (BA) to n (MMA): n (aibn) ═ 50: 100: 1, reacting for 6 hours at the reaction temperature of 120 ℃, and adding gamma-aminopropyl trimethoxy silane when the polymerization reaction is ended, wherein the adding amount of the silane is n (AIBN): n (methacryloyloxytrimethoxysilane) ═ 1: 1.1, continuing the reaction for 2 hours, removing the solvent after the reaction is finished, and carrying out GPC (GPC) test on the polymerization product. The number average molecular weight of the polymerization product was 26800 (design value 16400) and the molecular weight distribution was 2.20; the polymerization product was subjected to nuclear magnetic analysis, and the silane grafting ratio was 45% and was not completely located at the terminal position.
Compared with the examples, the first comparative example has the same molecular weight and molecular structure design, the molecular weight of the product of the traditional free radical polymerization is greatly different from the design value, the molecular weight distribution is wide, the traditional free radical polymerization is not easy to be made into a regular block structure, and the terminal group modification functionality is not easy to control.
Comparative example No. two
Firstly, two acrylate monomers of MMA and BA are pretreated, and an aluminum peroxide column is used for removing a polymerization inhibitor. According to a molar ratio n (BA): n (Ethylene bis (2-Bromoisobutyrate)): n (pmdeta): n (CuCl): 100: 1: 1.2: 1, sequentially adding all reactants into a 100mL single-neck flask, filling nitrogen for 30min, freezing by using liquid nitrogen, carrying out freezing-vacuumizing-unfreezing 5 times of circulation on a system, sealing, carrying out oil bath reaction at 90 ℃ for 12h, quickly introducing air and reducing the temperature to terminate the reaction to obtain a Br-PBA-Br double-end macroinitiator; taking Br-PBA-Br as an initiator, and similarly, adding the components in a certain molar ratio n (MMA): n (Br-PBA-Br): n (pmdeta): n (cucl) ═ 100: 1: 1.5: 1, synthesizing Br-PMMA-b-PBA-b-PMMA-Br according to the steps; the compound is prepared by mixing Br-PMMA-b-PBA-b-PMMA-Br, and n (methyl propenyl trimethoxy silane) in a certain molar ratio: n (Br-PMMA-b-PBA-b-PMMA-Br): n (pmdeta): n (cucl) ═ 10: 1: 1.5: 1, synthesizing silicon modified polyacrylate according to the steps, carrying out an aluminum peroxide column on a polymerization product obtained by the reaction, removing transition metal ions, and carrying out GPC test. Wherein the number average molecular weight of Br-PBA-Br is 13700 (design value 12800), the molecular weight distribution is 1.26, the number average molecular weight of Br-PMMA-b-PBA-b-PMMA-Br is 25300 (design value 22800), and the molecular weight distribution is 1.23; the number average molecular weight of the silicon modified polyacrylate is 27400, and the molecular weight distribution is 1.20; the final product had 80% siloxane capping rate by nuclear magnetic analysis.
In the second comparative example, the traditional Atom Transfer Radical Polymerization (ATRP) is adopted to synthesize the block copolymer, the size and the distribution of the molecular weight are ideal, but the reaction conditions are harsh and difficult to control. The terminal group modification is continuously carried out by adopting an ATRP (atom transfer radical polymerization) mode, so that higher silane end-capping rate can be achieved, but compared with the in-situ nucleophilic substitution reaction, the terminal group modification functionality is difficult to control, and the end group of the product obtained by polymerization contains halogen, so that the thermal stability is poor.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (27)
1. A preparation method of a terminal group modified polyacrylate block copolymer is characterized by comprising the following steps:
(1) carrying out electron transfer on a polymerization system comprising an acrylate monomer, an initiator, a catalyst, a ligand and a reducing agent to generate an atom transfer radical polymerization reaction of the catalyst, so as to prepare a polyacrylate block copolymer;
(2) carrying out in-situ end group modification on the polyacrylate block copolymer, and contacting with a nucleophilic reagent after or during the termination of the atom transfer radical polymerization reaction of the electron transfer generated catalyst to carry out nucleophilic substitution reaction to prepare the end group modified polyacrylate block copolymer;
the nucleophilic reagent is selected from silane compounds containing hydroxyl, amino or sulfhydryl;
the molar ratio of the end group halogen to the nucleophile in the polyacrylate block copolymer is 1: 1.1-1.3;
the reducing agent is selected from alcohols or reducing sugar;
in the step (1), the polymerization system further comprises an acid-binding agent.
2. The production method according to claim 1, wherein in the step (2), the reaction conditions of the nucleophilic substitution reaction are: the reaction temperature is 70-90 ℃, and the reaction time is 0.5-1 h.
3. The method of claim 1, wherein the nucleophile is selected from one or more of gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, and 3-amino-1-propanol.
4. The production method according to any one of claims 1 to 3, wherein the acrylate monomer is selected from one or more of (meth) acrylate esters of linear alcohols, (meth) acrylate esters of branched alcohols, and (meth) acrylate esters of alicyclic alcohols.
5. The method of claim 4, wherein the acrylate monomer is selected from one or more of C4-C15 (meth) acrylates.
6. The production method according to claim 4, the acrylate monomer is selected from one or more of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, 1, 2-ethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate.
7. The method according to claim 6, wherein the acrylate monomer is one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate.
8. The method of any one of claims 1-3, 5-7, wherein the initiator is selected from one or more of alkyl halides, benzyl halides, and α -halo esters.
9. The method according to claim 8, wherein the initiator is one or more selected from the group consisting of α -chlorophenyl ethane, α -bromophenylethane, ethyl α -bromoisobutyrate, and ethylene glycol dibromoisobutyrate.
10. The production method according to any one of claims 1 to 3, 5 to 7 and 9, wherein the catalyst is selected from the group consisting of transition metal halides; the transition metal in the transition metal halide is selected from one or more of copper, iron, nickel, chromium, manganese, cobalt and ruthenium.
11. The method according to claim 10, wherein the transition metal halide is one or more selected from the group consisting of cupric chloride, cupric bromide, and ferric chloride.
12. The method according to any one of claims 1 to 3, 5 to 7, 9 and 11, wherein the ligand is a compound containing nitrogen, oxygen, sulfur or phosphorus and capable of forming a metal-ligand complex by generating one or more coordinate bonds with the transition metal.
13. The method of claim 12, wherein the ligand is selected from one or more of bipyridine, triphenylphosphine, and N, N', N "-pentamethyldiethylenetriamine.
14. The production method according to any one of claims 1 to 3, 5 to 7, 9, 11 and 13, wherein the reducing agent is ethylene glycol.
15. The production method according to any one of claims 1 to 3, 5 to 7, 9, 11, 13,
the acid-binding agent is selected from one or more of sodium hydroxide, sodium bicarbonate and triethylamine.
16. The method of claim 15, wherein the acid-binding agent is selected from sodium bicarbonate or triethylamine.
17. The production method according to any one of claims 1 to 3, 5 to 7, 9, 11, 13 and 16, wherein the acrylate monomer: initiator: the molar ratio of the catalyst is 1000-10: 1: 0.1 to 1; the catalyst comprises the following components: ligand: reducing agent: the molar ratio of the acid-applying agent is 1: 1-2: 1-5: 1-5.
18. The method of claim 17, wherein the acrylate monomer: initiator: the molar ratio of the catalyst is 500-100: 1: 0.1-0.5;
the catalyst comprises the following components: ligand: reducing agent: the molar ratio of the acid-applying agent is 1: 1-1.2: 1.5-2: 1.5-2.
19. The production method according to any one of claims 1 to 3, 5 to 7, 9, 11, 13, 16 and 18, wherein the atom transfer radical polymerization of the electron transfer generating catalyst is bulk polymerization or solution polymerization.
20. The method according to claim 19, wherein the solvent in the solution polymerization is one or more selected from the group consisting of toluene, xylene, tetrahydrofuran, dichloromethane, N-dimethylamide, cyclohexanone, anisole, and dioxane.
21. The method according to claim 20, wherein the solvent in the solution polymerization is one or more selected from the group consisting of toluene, tetrahydrofuran, cyclohexanone and anisole.
22. The method according to claim 19, wherein the reaction temperature of the atom transfer radical polymerization reaction of the electron transfer generating catalyst is 25 to 150 ℃; the reaction time is 2-48 h.
23. The method according to claim 22, wherein the reaction temperature of the atom transfer radical polymerization reaction of the electron transfer generating catalyst is 50 to 90 ℃; the reaction time is 6-24 h.
24. A terminal-modified polyacrylate block copolymer prepared by the method of any one of claims 1-23.
25. A polyacrylate block copolymer obtained by the production method as described in any one of claims 1 to 23, wherein the number average molecular weight of the polyacrylate block copolymer is 500-100000 g/mol; the molecular weight distribution is 1-1.6.
26. The polyacrylate block copolymer of claim 25 wherein the number average molecular weight of the polyacrylate block copolymer is 5000-30000 g/mol; the molecular weight distribution is 1.1-1.3.
27. The polyacrylate block copolymer of claim 25 wherein the polyacrylate block copolymer is a 2-4 block copolymer.
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| CN109135630A (en) * | 2018-08-02 | 2019-01-04 | 常州大学 | A kind of moisture-curable silicone-containing based polyacrylic acid ester sealant and preparation method thereof |
| EP3702376B1 (en) * | 2018-09-24 | 2020-12-23 | Infineum International Limited | Method of making polymers |
| CN109503783B (en) * | 2018-12-10 | 2021-07-23 | 万华化学集团股份有限公司 | Terminal siloxane modified polyacrylate block copolymer and preparation method thereof |
| JP7516347B2 (en) * | 2019-03-20 | 2024-07-16 | 株式会社カネカ | Method for producing vinyl polymer |
| JP2023524454A (en) * | 2020-04-30 | 2023-06-12 | ダウ グローバル テクノロジーズ エルエルシー | Method for preparing olefin-acrylate block copolymers by ATRP |
| CN114940761B (en) * | 2022-06-20 | 2023-10-24 | 万华化学集团股份有限公司 | Furfural silane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (3)
| Title |
|---|
| 1、以醇作还原剂的AGET-ATRP 2、新型ESIPT半胱氨酸传感器的合成与性能研究;王严学;《中国博士学位论文全文数据库 工程科技I辑》;20140515(第05期);第1-2章 * |
| 电子转移生成催化剂的原子转移自由基聚合研究进展;崔瑾等;《中国胶粘剂》;20151130;第24卷(第11期);第50-54页 * |
| 端羟基星形丙烯酸酯树脂的制备及涂料性能;赵雯等;《高分子材料科学与工程》;20161130;第32卷(第11期);第7-11页 * |
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