CN114181348B - Full-bio-based bottle brush-shaped thermoplastic elastomer and preparation method thereof - Google Patents
Full-bio-based bottle brush-shaped thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN114181348B CN114181348B CN202111564252.3A CN202111564252A CN114181348B CN 114181348 B CN114181348 B CN 114181348B CN 202111564252 A CN202111564252 A CN 202111564252A CN 114181348 B CN114181348 B CN 114181348B
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 102
- 229920002101 Chitin Polymers 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 68
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- 239000012986 chain transfer agent Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- 241001264766 Callistemon Species 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 15
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 claims description 3
- FRXLFVNGTPQFEJ-UHFFFAOYSA-N 3-bromopropanoyl bromide Chemical compound BrCCC(Br)=O FRXLFVNGTPQFEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- 230000015572 biosynthetic process Effects 0.000 description 48
- 238000003786 synthesis reaction Methods 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 229920001971 elastomer Polymers 0.000 description 41
- 229920006392 biobased thermoplastic Polymers 0.000 description 39
- 239000000806 elastomer Substances 0.000 description 39
- 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 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 25
- 235000012141 vanillin Nutrition 0.000 description 25
- 239000000463 material Substances 0.000 description 22
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 17
- 239000003921 oil Substances 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 239000000376 reactant Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 9
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 8
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- PRNCMAKCNVRZFX-UHFFFAOYSA-N 3,7-dimethyloctan-1-ol Chemical compound CC(C)CCCC(C)CCO PRNCMAKCNVRZFX-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 6
- -1 alcohol ester Chemical class 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-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
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229940049964 oleate Drugs 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- 229920000263 Rubber seed oil Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 3
- 239000002383 tung oil Substances 0.000 description 3
- KLFDZFIZKMEUGI-UHFFFAOYSA-M 1-methyl-3-prop-2-enylimidazol-1-ium;bromide Chemical compound [Br-].C[N+]=1C=CN(CC=C)C=1 KLFDZFIZKMEUGI-UHFFFAOYSA-M 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 2
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- ASAPXSLRMDUMFX-QXMHVHEDSA-N [(z)-octadec-9-enyl] prop-2-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)C=C ASAPXSLRMDUMFX-QXMHVHEDSA-N 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 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 description 2
- 230000009982 effect on human Effects 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 description 1
- ILLHORFDXDLILE-UHFFFAOYSA-N 2-bromopropanoyl bromide Chemical compound CC(Br)C(Br)=O ILLHORFDXDLILE-UHFFFAOYSA-N 0.000 description 1
- WVXMNBDPVYOPLX-UHFFFAOYSA-N 2-isocyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCC[N+]#[C-] WVXMNBDPVYOPLX-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical group OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a full-biobased bottle brush-shaped thermoplastic elastomer, which relates to the technical field of thermoplastic elastomers and has the following structural formula:
the invention also provides a preparation method of the all-biobased bottle brush-shaped thermoplastic elastomer. The invention has the beneficial effects that: the all-bio-based bottle brush-shaped thermoplastic elastomer disclosed by the invention is excellent in mechanical property, has the strain of more than 500%, has good biocompatibility, can be naturally degraded and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of thermoplastic elastomers, in particular to a full-biobased bottle brush-shaped thermoplastic elastomer and a preparation method thereof.
Background
The thermoplastic elastomer has elasticity similar to rubber, can be molded and processed by injection molding, extrusion molding, hot press molding and other modes like plastic, combines the two advantages of excellent elasticity of rubber and easy molding and processing of plastic, and is widely applied to industries such as automobile parts, building materials, medical instruments, sealing products, sports equipment, electronic products and the like while being paid attention by scientific researchers.
However, most of thermoplastic elastomers are prepared from non-renewable petroleum-based resources, and in recent years, energy exhaustion and increasingly severe environmental pollution problems are troubling countless researchers. The extraction of "green" chemicals and materials from renewable biomass materials, replacing petroleum-based polymers currently in widespread use, is considered an effective solution to the current problem.
Therefore, people simply modify some natural resources and derivatives thereof, such as vegetable oil, rosin, vanillin, terpenes and the like, and prepare a series of biodegradable monomers capable of being used for polymerization to replace petroleum-based monomers and prepare bio-based thermoplastic elastomers so as to get rid of excessive dependence on non-renewable resources.
However, the mechanical properties of the bio-based thermoplastic elastomer material are poor, and some nano materials are usually required to be filled to reinforce the bio-based thermoplastic elastomer material, or covalent or non-covalent interactions are introduced to obtain a thermoplastic elastomer material with excellent properties, so that how to prepare the high-performance bio-based thermoplastic elastomer material becomes a hot problem of research.
The bottle brush-shaped graft polymer can control the self micro topological structure by adjusting the lengths of the main chain and the side chain, the grafting density of the side chain and the like, thereby realizing the regulation and control of the mechanical property. For example, patent publication No. CN111187385A discloses a cellulose-based bottle brush-shaped thermoplastic elastomer, which combines cellulose with organic molecules to form a thermoplastic elastomer, but has a strain of only about 160% at the maximum.
Disclosure of Invention
The invention aims to provide a novel all-biobased bottle brush-shaped thermoplastic elastomer and a preparation method thereof, wherein the thermoplastic elastomer has good ductility and mechanical properties.
The invention solves the technical problems through the following technical means:
a full bio-based bottle brush-shaped thermoplastic elastomer has the following structural formula:
wherein n is more than or equal to 50 and less than or equal to 200, m is more than or equal to 100 and less than or equal to 1000, l is more than or equal to 0 and less than or equal to 1000, R 1 Is composed of
Any one of the groups;
R 2 comprises the following steps:
R 3 comprises the following steps:
Has the beneficial effects that: the all-bio-based bottle brush-shaped thermoplastic elastomer disclosed by the invention is excellent in mechanical property, and the strain reaches more than 500%. The main chain of the chitin has a large amount of ester bonds, all monomers of the side chain have ester bond structures, and the ester bonds can be well broken and degraded under natural conditions, so that the chitin has good biocompatibility and is environment-friendly.
The full-bio-based bottle brush-shaped thermoplastic elastomer takes chitin which is a natural biomass material as a rigid main chain, a series of bio-based monomers are grafted, the rigid chitin serves as a cross-linking point in the whole polymer system, and the long-carbon-chain bio-based monomers endow the polymer network with good chain flexibility and ductility.
The method for preparing the all-bio-based bottle brush-shaped thermoplastic elastomer comprises the following steps:
(1) adding a chitin macromolecular chain transfer agent, a reaction monomer A, a reaction monomer B and an initiator into a reaction bottle with a mixed solvent;
(2) removing water and air in the reaction bottle, reacting at 60-100 ℃, and collecting and drying a product after the reaction is finished;
the structural formula of the chitin macromolecular chain transfer agent is as follows:
has the advantages that: the invention takes chitin, a natural biomass material, as a rigid main chain, and grafts a series of bio-based monomers, the rigid chitin serves as a cross-linking point in the whole polymer system, and the long-carbon-chain bio-based monomers endow the polymer network with good chain flexibility and ductility.
The invention can realize the adjustment of the microscopic topological structure of the polymer network by designing the type of the reaction monomer, the grafting density, the relative proportion of the rigid main chain and the grafted side chain and the like, thereby obtaining the environment-friendly full-biology-based bottle brush-shaped thermoplastic elastomer material with excellent macroscopic mechanical property, good biocompatibility and natural degradation.
The prepared all-bio-based bottle brush-shaped thermoplastic elastomer has excellent mechanical property, the strain reaches more than 500 percent, the main chain of the chitin has a large amount of ester bonds, all monomers of the side chain have ester bond structures, the ester bonds can be well broken and degraded under natural conditions, and the all-bio-based bottle brush-shaped thermoplastic elastomer has good biocompatibility, and the adopted raw materials are all natural biomass sources and have no toxic or side effect on human bodies, so that the prepared material can be naturally degraded and is environment-friendly.
The preparation route of the full-biobased bottle brush-shaped thermoplastic elastomer is as follows:
preferably, the method for preparing the all-bio-based bottle brush-shaped thermoplastic elastomer specifically comprises the following steps:
(1) adding 1-10 parts by weight of chitin macromolecular chain transfer agent, 250-5200 parts by weight of reaction monomer A, 0-700 parts by weight of reaction monomer B and 0.015-0.3 part by weight of initiator into a reaction bottle containing 445-7500 parts by weight of mixed solvent;
(2) and (3) removing water and air in the reaction flask, reacting at 60-100 ℃, and collecting and drying the product after the reaction is finished.
Has the advantages that: the higher the rigid chain proportion in the product, the better the mechanical strength. The relative proportion of the rigid main chain and the grafted side chain in the reaction product can be controlled by adjusting the proportion of the reaction monomer and the chitin macromolecular chain transfer agent, the larger the proportion of the reaction monomer to the chain transfer agent is, the higher the proportion of the side chain in the material is, and the reaction monomer A and the reaction monomer B are selected to ensure that the product has different physicochemical properties.
Preferably, the reactive monomer a is:
Preferably, the reactive monomer a is lauryl acrylate.
Preferably, the reactive monomer B is:
any one or more groups of (a).
Preferably, the reactive monomer B is vanillin acrylate.
Preferably, the initiator in the step (1) is azobisisobutyronitrile.
Preferably, the mixed solvent in the step (1) is prepared from N, N-dimethylformamide and 1, 4-dioxane in a volume ratio of 6: 4.
Preferably, in the step (2), the reaction flask is subjected to a freeze-vacuum-thawing cycle, after the reaction is carried out for 12 to 48 hours at the temperature of between 60 and 100 ℃, the reaction flask is placed in a precipitating agent for precipitation and collection, and then the collected product is placed in a vacuum drying mode at the temperature of between 50 and 80 ℃.
Preferably, the precipitant is a mixed solution of methanol and water.
Preferably, the preparation method of the chitin macromolecular chain transfer agent in the step (1) comprises the following steps:
(a) mixing 1-10 parts by weight of chitin and 40-600 parts by weight of 1-allyl-3-methylimidazole bromide ionic liquid until the chitin is completely dissolved in the 1-allyl-3-methylimidazole bromide ionic liquid to form a solution;
(b) placing the solution in the step (1) in an ice-water bath, slowly dropwise adding 50-600 parts by weight of bromopropionyl bromide, removing the ice-water bath after dropwise adding is finished, reacting at room temperature, and after the reaction is finished, precipitating, washing and drying to obtain a chitin initiator;
(c) dissolving 1-10 parts by weight of chitin initiator in 25-240 parts by weight of dimethyl sulfoxide, simultaneously dissolving 0.2-3 parts by weight of benzyl mercaptan, 0.4-6 parts by weight of carbon disulfide and 0.2-3 parts by weight of triethylamine in 6-60 parts by weight of dimethyl sulfoxide, mixing the two mixed solutions, reacting at 40 ℃, and after the reaction is finished, precipitating, washing and drying to obtain the chitin chain transfer agent.
Has the advantages that: the grafting density of the product is adjusted by controlling the adding amount of mercaptan, carbon disulfide and triethylamine reactants, and the more the three reactants are fed, the higher the grafting density is.
Preferably, 1-10 parts by weight of chitin and 40-600 parts by weight of 1-allyl-3-methylimidazolium bromide ionic liquid in the step (a) are added into a round-bottom flask, and the round-bottom flask is heated to 100-120 ℃ while water and air in the round-bottom flask are pumped out by an oil pump.
The reaction formula of the chitin macromolecular chain transfer agent is as follows:
preferably, the reaction in step (b) is carried out at room temperature for 48-72h, then precipitated in pure water and dried under vacuum at 50-80 ℃ overnight.
Preferably, the two mixed solutions in step (c) are mixed and reacted at 40 ℃ for 12-24h, then precipitated in pure water, washed, and dried in vacuum at 50-80 ℃ overnight.
The invention has the advantages that: the all-biobased bottle brush-shaped thermoplastic elastomer disclosed by the invention is excellent in mechanical property, and the strain reaches more than 500%. The chitin main chain has a large number of ester bonds, all monomers of the side chain have ester bond structures, and the ester bonds can be broken and degraded well under natural conditions, have good biocompatibility, can be naturally degraded, and are environment-friendly.
The full-bio-based bottle brush-shaped thermoplastic elastomer takes chitin which is a natural biomass material as a rigid main chain, a series of bio-based monomers are grafted, the rigid chitin serves as a cross-linking point in the whole polymer system, and the long-carbon-chain bio-based monomers endow the polymer network with good chain flexibility and ductility. The raw materials adopted by the invention are all natural biomass sources, and have no toxic or side effect on human bodies, so that the prepared material can be naturally degraded and is environment-friendly.
The invention can realize the adjustment of the microscopic topological structure of the polymer network by designing the type of the reaction monomer, the grafting density, the relative proportion of the rigid main chain and the grafted side chain and the like, thereby obtaining the environment-friendly full-biology-based bottle brush-shaped thermoplastic elastomer material with excellent macroscopic mechanical property, good biocompatibility and natural degradation.
The higher the rigid chain proportion in the product, the better the mechanical strength. The relative proportion of the rigid main chain and the grafted side chain in the reaction product can be controlled by adjusting the proportion of the reaction monomer and the chitin macromolecular chain transfer agent, the larger the proportion of the reaction monomer to the chain transfer agent is, the higher the proportion of the side chain in the material is, and the reaction monomer A and the reaction monomer B are selected to ensure that the product has different physicochemical properties.
The grafting density of the product is adjusted by controlling the adding amount of mercaptan, carbon disulfide and triethylamine reactants, and the more the three reactants are fed, the higher the grafting density is.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of monomer A11 according to example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of monomer A18 according to example 2 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of monomer B1 according to example 3 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of monomer B3 according to example 4 of the present invention;
FIG. 5 is a nuclear magnetic hydrogen spectrum of the chitin macroinitiator according to example 5 of the present invention;
FIG. 6 is a nuclear magnetic hydrogen spectrum of the chitin macromolecular chain transfer agent according to example 6 of the present invention;
FIG. 7 is a nuclear magnetic hydrogen spectrum of the all bio-based bottle brush type thermoplastic elastomer 1 according to example 7 of the present invention;
FIG. 8 is a nuclear magnetic hydrogen spectrum of the thermoplastic elastomer 6 with a bottle brush shape based on the total biology in the embodiment 12 of the invention;
FIG. 9 is a nuclear magnetic hydrogen spectrum of the all bio-based bottle brush polymer 9 of comparative example 1 of the present invention;
FIG. 10 is a nuclear magnetic hydrogen spectrum of the all bio-based bottle brush thermoplastic elastomer 10 according to example 15 of the present invention;
FIG. 11 is a nuclear magnetic hydrogen spectrum of the all bio-based bottle brush thermoplastic elastomer 11 according to example 16 of the present invention;
FIG. 12 is a nuclear magnetic hydrogen spectrum of the all bio-based bottle brush thermoplastic elastomer 12 according to example 17 of the present invention;
fig. 13 is an infrared spectrum of the product of chitin according to the present invention, example 5-example 7, example 12 and comparative example 1;
FIG. 14 is an IR spectrum of the product of example 10 to example 13 according to the present invention;
fig. 15 is thermogravimetric analysis spectra of chitin according to the present invention, example 5-example 7, example 10 and comparative example 1;
fig. 16 is a thermogravimetric analysis first order differential spectrum of chitin of the present invention, example 5-example 7, example 10 and comparative example 1;
FIG. 17 is a differential scanning calorimetry plot of the products of example 7, example 10 and comparative example 1 of the present invention;
FIG. 18 is a differential scanning calorimetry plot of the product of example 8-example 14 of the present invention;
FIG. 19 is a mechanical tensile diagram of the product of example 11 of the present invention;
FIG. 20 is a mechanical tensile diagram of the product of example 12 of the present invention.
FIG. 21 is a mechanical tensile diagram of the product of example 18 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The synthesis of the reactive monomer A11 specifically comprises the following steps:
33.92g of 4-chloromethylstyrene and 57.06g of oleic acid are dissolved in 100ml of N, N-dimethylformamide solution, stirred uniformly, and finally 23.04g of 1,1,3, 3-tetramethylguanidine is added, and the reaction is carried out at 60 ℃ for more than 12 hours. After the reaction was completed, 200ml of ethyl acetate was added to dilute the reaction mixture. Washed several times with saturated sodium chloride solution and pure water. And removing residual polymerization inhibitor in the product by using alkaline alumina, and removing dichloromethane by rotary evaporation to obtain the 4-chloromethyl styrene oleate monomer.
Example 2
The synthesis of the reactive monomer A18 specifically comprises the following steps:
15.83g of tetrahydrogeraniol and 10.73g of triethylamine were dissolved in 100ml of dichloromethane, and then 9.9g of acryloyl chloride were slowly added dropwise in an ice-water bath. After completion of the dropwise addition, the reaction was carried out at room temperature for 48 hours, and the product was filtered to remove insoluble solids, and washed with a saturated sodium bicarbonate solution, a saturated sodium chloride solution and pure water, respectively, several times. And removing residual polymerization inhibitor in the product by using alkaline alumina, and removing dichloromethane by rotary evaporation to obtain the acrylic acid tetrahydrochysene alcohol ester monomer.
Example 3
The synthesis of the reactive monomer B1 specifically comprises the following steps:
20g of vanillin and 14.34g of triethylamine are dissolved in 150ml of dichloromethane, and then 12.82g of acryloyl chloride are slowly added dropwise in an ice-water bath. After completion of the dropwise addition, the reaction was carried out at room temperature for 48 hours, and the product was filtered to remove insoluble solids, and washed with a saturated sodium bicarbonate solution, a saturated sodium chloride solution and pure water, respectively, several times. And removing residual polymerization inhibitor in the product by using alkaline alumina, and removing dichloromethane by rotary evaporation to obtain the vanillin acrylate monomer.
Example 4
The synthesis of the reactive monomer B3 specifically comprises the following steps:
15.28g of salicylaldehyde and 13.41g of triethylamine were dissolved in 130ml of dichloromethane, and then 12.38g of acryloyl chloride was slowly added dropwise in an ice-water bath. After completion of the dropwise addition, the reaction was carried out at room temperature for 48 hours, and the product was filtered to remove insoluble solids, and washed with a saturated sodium bicarbonate solution, a saturated sodium chloride solution and pure water, respectively, several times. And removing residual polymerization inhibitor in the product by using alkaline alumina, and removing dichloromethane by rotary evaporation to obtain the salicylaldehyde acrylate monomer.
Example 5
The synthesis of the chitin initiator specifically comprises the following steps:
6g of chitin and 330g of 1-allyl-3-methylimidazolium bromide ionic liquid are added into a flask, the flask is heated to 100 ℃, and simultaneously, an oil pump is used for pumping out water in the flask until the chitin is completely dissolved to form a brown yellow transparent solution. Then the flask was cooled to room temperature, placed in an ice-water bath, and 285g of 2-bromopropionyl bromide solution was slowly added dropwise thereto, after completion of the addition, reacted at room temperature for 48 hours. The product was precipitated in a large amount of water, washed several times, and dried under vacuum at 60 ℃ to give 10.16g of chitin initiator (degree of polymerization n-80).
Example 6
The synthesis of the chitin macromolecular chain transfer agent specifically comprises the following steps:
4g chitin macroinitiator was dissolved in 80ml dimethyl sulfoxide while 669mg benzyl mercaptan, 545mg triethylamine and 1.23g carbon disulfide were dissolved in 20ml dimethyl sulfoxide and stirred. And after the substances are completely dissolved and the solution is uniform, mixing the two solutions, and reacting for 12 hours at 40 ℃. Precipitation in water and drying gave 3.56g of chitin macromolecular chain transfer agent (degree of polymerization n: 74).
Example 7
Synthesis of all-biobased thermoplastic elastomer 1
To a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, 47mg of the chitin macromolecular chain transfer agent of example 6, 6.01g of lauryl acrylate and 0.82mg of azobisisobutyronitrile were added, and after three cycles of freezing-vacuum-melting were repeated, a Schlenk reaction flask was evacuated and sealed and placed in an oil bath. After 12 hours of reaction at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure at 50 ℃ in a vacuum oven to obtain 5.3g of all-bio-based bottle brush-like thermoplastic elastomer 1(n ═ 74, m ═ 437, l ═ 0).
Example 8
Synthesis of all-biobased thermoplastic elastomer 2
47mg of chitin macromolecular chain transfer agent, 3.61g of lauryl acrylate, 2.06g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeated, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath. After 12 hours of reaction at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to obtain 4.93g of all-bio-based thermoplastic elastomer 2(n ═ 74, m ═ 259, l ═ 172).
Example 9
Synthesis of all-biobased thermoplastic elastomer 3
47mg of chitin macromolecular chain transfer agent, 3.3g of lauryl acrylate, 2.32g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeatedly carried out, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath kettle. After 12 hours of reaction at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure in a vacuum oven at 50 ℃ to obtain 4.89g of all-bio-based thermoplastic elastomer 3(n ═ 74, m ═ 237, l ═ 194).
Example 10
Synthesis of all-biobased thermoplastic elastomer 4
47mg of chitin macromolecular chain transfer agent, 3.00g of lauryl acrylate, 2.58g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeated, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath kettle. After 12 hours of reaction at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure in a vacuum oven at 50 ℃ to obtain 5.01g of a total bio-based thermoplastic elastomer 4 (chitin content: 0.94 wt%) (n ═ 74, m ═ 222, l ═ 223).
Example 11
Synthesis of all-biobased thermoplastic elastomer 5
47mg of chitin macromolecular chain transfer agent, 2.70g of lauryl acrylate, 2.83g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeated, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath kettle. After 12 hours at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure in a vacuum oven at 50 ℃ to obtain 4.39g of a total bio-based thermoplastic elastomer 5 (chitin content: 1.07 wt%) (n ═ 74, m ═ 176, and l ═ 216).
Example 12
Synthesis of all-biobased thermoplastic elastomer 6
47mg of chitin macromolecular chain transfer agent, 2.40g of lauryl acrylate, 3.09g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeated, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath kettle. After 12 hours at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to obtain 4.44g of the all-bio-based thermoplastic elastomer 6 (n: 74, m: 160, l: 240).
Example 13
Synthesis of all-biobased thermoplastic elastomer 7
47mg of chitin macromolecular chain transfer agent, 1.80g of lauryl acrylate, 3.61g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeated, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath. After 12 hours at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to obtain 4.42g of the total bio-based thermoplastic elastomer 7 (n: 74, m: 121, l: 283).
Example 14
Synthesis of all-biobased thermoplastic elastomer 8
47mg of chitin macromolecular chain transfer agent, 1.2g of lauryl acrylate, 4.12g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeated, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath kettle. After 12 hours at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to obtain 4.20g of a total bio-based thermoplastic elastomer 8(n ═ 74, m ═ 79, l ═ 316).
Comparative example 1
Synthesis of all-biobased Polymer 9
47mg of chitin macromolecular chain transfer agent, 5.15g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeated, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath kettle. After 12h at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to give 4.22g of all-bio-based polymer 9(n ═ 74, m ═ 0, l ═ 405).
Example 15
Synthesis of all-biobased thermoplastic elastomer 10
47mg of chitin macromolecular chain transfer agent, 10.6g of tetrahydrogeranyl acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 18ml of N, N-dimethylformamide and 12ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeatedly carried out, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath kettle. After 12h at 70 ℃, the reaction was stopped and the reaction was stopped in a large amount of methanol: the resulting precipitate was precipitated in a mixed solution of water (2:8), and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to obtain 3.03g of a total bio-based thermoplastic elastomer 10 (n: 74, m: 703, l: 0).
Example 16
Synthesis of all-biobased thermoplastic elastomer 11
25.75mg of chitin macromolecular chain transfer agent, 2.65g of tetrahydrogeranyl acrylate, 2.25g of salicylaldehyde acrylate in example 4 and 0.82mg of azobisisobutyronitrile were added to a mixed solution prepared from 7.5ml of N, N-dimethylformamide and 5ml of 1, 4-dioxane, and after three freezing-vacuum-melting cycles were repeated, a Schlenk reaction flask was evacuated and sealed and placed in an oil bath. After 12 hours at 70 ℃, the reaction was stopped, precipitated into a large amount of methanol solution, and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to obtain 2.34g of the all-bio-based thermoplastic elastomer 11(n ═ 66, m ═ 295, and l ═ 295).
Example 17
Synthesis of fully biobased thermoplastic elastomer 12
To a mixed solution of 15ml of N, N-dimethylformamide and 10ml of 1, 4-dioxane, 25.75mg of a chitin macromolecular chain transfer agent, 9.98g of 4-chloromethylstyrene oleate and 0.82mg of azobisisobutyronitrile in example 1 were added, and after three cycles of freezing-vacuum-melting were repeated, a Schlenk reaction flask was placed in an oil bath under vacuum and sealed conditions. After 12 hours of reaction at 70 ℃, the reaction was stopped, and the product was precipitated in a large amount of methanol solution and dried in a vacuum oven at 50 ℃ under reduced pressure to obtain 5.96g of the total bio-based thermoplastic elastomer 12(n ═ 66, m ═ 744, l ═ 0).
Example 18
Synthesis of all-biobased thermoplastic elastomer 13
94mg of chitin macromolecular chain transfer agent, 2.40g of lauryl acrylate, 3.09g of vanillin acrylate and 0.82mg of azobisisobutyronitrile are added into a mixed solution prepared from 12ml of N, N-dimethylformamide and 8ml of 1, 4-dioxane, and after three times of freezing-vacuum-melting cycles are repeated, a Schlenk reaction bottle is vacuumized and sealed and placed in an oil bath kettle. After 12 hours at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure in a vacuum oven at 50 ℃ to obtain 4.43g of a total bio-based thermoplastic elastomer 13 (chitin content: 2.12 wt%) (n ═ 74, m ═ 79, l ═ 118).
Example 19
Synthesis of fully biobased thermoplastic elastomer 14
The preparation was carried out in the same manner as in application example 7, except that the reactant was oleyl acrylate (A16).
Example 20
Synthesis of all-biobased thermoplastic elastomer 15
The preparation was carried out in the same manner as in application example 16, except that the reactants were oleyl acrylate and vanillin acrylate.
Example 21
Synthesis of fully biobased thermoplastic elastomer 16
The preparation process was the same as in application example 7, except that the reactant was tung oil acrylate (A10).
Example 22
Synthesis of all-biobased thermoplastic elastomer 17
The preparation process was the same as in application example 16, except that the reactants were tung oil acrylate and salicylaldehyde acrylate.
Example 23
Synthesis of fully biobased thermoplastic elastomer 18
The preparation was carried out in the same manner as in application example 16, except that the reactants were tetrahydrogeranyl acrylate and isobornyl acrylate.
Example 24
Synthesis of all-biobased thermoplastic elastomer 19
The preparation method was the same as in application example 16, except that the reactants were tetrahydrogeranyl acrylate and tetrahydrofurfuryl acrylate.
Example 25
Synthesis of all-biobased thermoplastic elastomer 20
The procedure was as in application example 16, except that the reactants were lauryl acrylate and isobornyl acrylate.
Example 26
Synthesis of all-biobased thermoplastic elastomer 21
The preparation was carried out in the same manner as in application example 16, except that the reactants were lauryl acrylate and tetrahydrofurfuryl acrylate.
Example 27
Synthesis of fully biobased thermoplastic elastomer 22
The preparation was carried out in the same manner as in application example 16 except that the reactants were 4-chloromethylstyrene oleate and isobornyl acrylate.
Example 28
Synthesis of all-bio-based thermoplastic elastomer 23
The preparation process was the same as in application example 16, except that the reactants were 4-chloromethylstyrene oleate and tetrahydrofurfuryl acrylate.
Example 29
The synthesis of the reaction monomers A1, A2 and A3 specifically comprises the following steps:
80g of rubber seed oil are taken and heated to 100 ℃ while purging with nitrogen for 4 h. The temperature was reduced to 60 ℃ and 30.35g of 3-aminopropanol and 0.6ml of sodium methoxide (5mol/L) were added to react at 60 ℃ overnight. After the reaction, the reaction mixture was diluted with 250ml of dichloromethane, washed with saturated brine several times, dried over anhydrous sodium sulfate, and finally dichloromethane was removed by rotary evaporation to obtain 92.5g of a precursor.
50g of the precursor, 18.3g of acrylic anhydride and 0.18g of 4-dimethylaminopyridine were reacted at 60 ℃ overnight, and 5ml of deionized water and 10ml of tetrahydrofuran were added to continue the reaction for 4 hours. After the reaction was completed, the reaction mixture was diluted with 200ml of dichloromethane, washed with a saturated aqueous sodium bicarbonate solution and a saturated common salt solution several times, dried over anhydrous sodium sulfate, and finally dichloromethane was removed by rotary evaporation to obtain 51.9g of a monomer (A1, A2 and A3 mixture).
Example 30
Synthesis of reaction monomers A2, A3 and A4, which were prepared in the same manner as in application example 29, except that the raw rubber seed oil was changed to palm oil.
Example 31
The synthesis of the reactive monomer A5 specifically comprises the following steps:
80g of tung oil are taken and heated to 100 ℃ while purging with nitrogen for 4 h. The temperature was reduced to 60 ℃ and 30.35g of 3-aminopropanol and 0.6ml of sodium methoxide (5mol/L) were added thereto and the mixture was reacted overnight at 60 ℃. After completion of the reaction, the reaction mixture was diluted with 250ml of dichloromethane, washed with saturated brine several times, dried over anhydrous sodium sulfate, and finally dichloromethane was removed by rotary evaporation to obtain 91.8g of a precursor.
50g of the precursor, 18.3g of acrylic anhydride and 0.18g of 4-dimethylaminopyridine were reacted at 60 ℃ overnight, and 5ml of deionized water and 10ml of tetrahydrofuran were added to continue the reaction for 4 hours. After the reaction was completed, the mixture was diluted with 200ml of dichloromethane, washed with a saturated aqueous sodium bicarbonate solution and a saturated brine several times, dried over anhydrous sodium sulfate, and finally dichloromethane was removed by rotary evaporation to obtain 54.2g of a monomer.
Then 36.3g of monomer is taken, 9.8g of maleic anhydride is added, and the mixture is condensed and refluxed for 12 hours at 130 ℃. After the reaction was completed, the reaction mixture was diluted with 150ml of dichloromethane. The mixture was washed with a saturated aqueous sodium hydrogencarbonate solution and saturated brine several times, dried over anhydrous sodium sulfate, and finally methylene chloride was removed by rotary evaporation to obtain 41.3g of monomer A5.
Example 32
Synthesis of reaction monomers A6, A7 and A8, which were prepared in the same manner as in application example 29, except that the starting material, 3-aminopropanol, was changed to 2- (methylamino) ethanol.
Example 33
Synthesis of reaction monomers A7, A8 and A9, which were prepared in the same manner as in application example 29, except that the raw material rubber seed oil and 3-aminopropanol were changed to palm oil and 2- (methylamino) ethanol.
Example 34
Synthesis of reaction monomer A10, which was prepared in the same manner as in application example 31, except that the starting material 3-aminopropanol was changed to 2- (methylamino) ethanol.
Example 35
Synthesis of reaction monomer A12, which was prepared in the same manner as in application example 1, except that the starting material 4-chloromethylstyrene was changed to chloroethyl acrylate.
Example 36
Synthesis of reaction monomer A13, the preparation method was the same as in application example 1, except that the starting material oleic acid was changed to ricinoleic acid.
Example 37
Synthesis of reaction monomer A14, the preparation method was the same as in application example 1, except that the starting materials oleic acid and 4-chloromethylstyrene were changed to ricinoleic acid and chloroethyl acrylate.
Example 38
Synthesis of reaction monomer A16, the preparation method was the same as in application example 2, except that the starting material tetrahydrogeraniol was changed to oleyl alcohol.
Example 39
Synthesis of reaction monomer A17, the preparation method was the same as in application example 2, except that cardanol was used instead of tetrahydrogeraniol as a raw material.
Example 40
Synthesis of reaction monomer B5, the preparation method was the same as in application example 3, except that the raw material vanillin was replaced with 5-hydroxymethylfurfural.
EXAMPLE 41
The synthesis of the reactive monomer B6 specifically comprises the following steps:
4g of sodium hydroxide was dissolved in 500ml of anhydrous methanol, and then 17.62g of 4-methylumbelliferone was added to the solution, and dissolved by heating at 60 ℃ for 30 min. Cooling to room temperature, and refrigerating at 0-5 deg.C. Subsequently, 10.37g of acryloyl chloride was slowly added dropwise in an ice-water bath, and the reaction was carried out for 2 hours. The product was precipitated in ice water and washed, collected and dried under vacuum at 60 ℃.
Example 42
The synthesis of the reactive monomer B7 specifically comprises the following steps:
16g of 2-amino-4-hydroxy-6-methylpyrimidine was added to 80ml of dimethyl sulfoxide and dissolved by heating at 160 ℃. Then, 22g of isocyanoethyl acrylate was added to the solution, and reacted for 30 min. After the reaction was complete, the product was precipitated in acetone. The product was collected and dried under vacuum at 30 ℃ to give monomer B7. The reaction monomers a15, B2, B4 were obtained commercially.
Experimental data and analysis: FIGS. 1 to 12 are nuclear magnetic hydrogen spectra of the products of example 1 to example 7, example 12, comparative example 1, example 15 to example 17, respectively. In the figure, a, b, c, d and the like represent the peak positions of the groups, and it can be seen that all the groups have corresponding peaks in the nuclear magnetism of the obtained product, thereby powerfully proving the correct synthesis of the product.
FIG. 13 is an IR spectrum of chitin, example 5, example 6, comparative example 1, example 12 and example 7; FIG. 14 is an IR spectrum as reported in example 10, example 11, example 12 and example 13; it can be seen that 1740cm appears in the infrared of the products obtained in examples 5 and 6 compared with the original chitin -1 The peaks indicate the presence of ester groups in the product, thus demonstrating the successful synthesis of initiators and chain transfer agents.
2850cm in the Infrared of the product obtained in example 7 -1 And 2920cm -1 The presence of a large number of carbon-hydrogen bonds, 1730cm -1 The presence of ester groups, thus demonstrating the successful synthesis of polylauryl acrylate.
1030cm in the infrared of the product obtained in comparative example 1 -1 And 1265cm -1 Peak of (2), demonstrating the presence of ether linkages, 1762cm -1 And 1700cm -1 The presence of an ester group, thus confirmingSuccessful synthesis of vanillin acrylic acid.
In example 10, example 11, example 12 and example 13, characteristic peaks (2850 cm) of lauryl acrylate were simultaneously observed -1 ，2920cm -1 And 1730cm -1 ) And characteristic peaks of vanillin acrylate (1030 cm) -1 ，1265cm -1 ，1762cm -1 And 1700cm -1 ) Thus proving the successful synthesis of both copolymers.
Fig. 15 is thermogravimetric analysis spectra of chitin, example 5-example 7, example 10 and comparative example 1; fig. 16 shows thermogravimetric analysis first-order differential spectra of chitin, examples 5-7, example 10 and comparative example 1, and it can be seen that the thermal stability of examples 5 and 6 is reduced compared with pure chitin material after modification. In the obtained polymer, the comparison of example 7, example 10 and comparative example 1 shows that the polylauryl acrylate starts to degrade firstly, and the thermal stability is poor; the polyacrylic vanillin ester is more stable than the polyacrylic vanillin ester, and the thermal stability of the product obtained by copolymerizing the polyacrylic vanillin ester and the polyacrylic vanillin ester is between the two thermal stabilities.
FIG. 17 is a differential scanning calorimetry plot for example 7, example 10 and comparative example 1. FIG. 18 is a differential scanning calorimetry plot of the products of example 8-example 14. It can be seen that the glass transition temperature of the polyacrylate vanillin is higher than that of the polyacrylate lauryl, the glass transition temperature of the product obtained by copolymerizing the polyacrylate vanillin and the polyacrylate lauryl is between the glass transition temperature of the product and the glass transition temperature of the product increases with the increase of the content of vanillin acrylate.
FIG. 19 is a mechanical tensile diagram of example 11, which shows that the strain of the bio-based thermoplastic elastomer material in the form of a bottle brush reaches 2600% or more and the stress reaches about 0.5 MPa. The material obtained by the invention has good ductility and certain mechanical strength.
FIG. 20 is a mechanical tensile diagram of example 12, which shows that the strain of the all-bio based bottle brush-shaped thermoplastic elastomer material obtained in example 12 is more than 500% and the stress is about 3.2 MPa. The material obtained by the method has good mechanical properties, and the high-performance all-biobased bottle brush-shaped thermoplastic elastomer material is successfully prepared. Meanwhile, the chitin content of the embodiment 11 and the chitin content of the embodiment 12 are both about 1 wt%, and the higher the content of the vanillin acrylic ester with high glass transition temperature of the embodiment 12 is, the better the mechanical property is.
FIG. 21 is a mechanical tensile diagram of example 18, which shows that the all-bio based thermoplastic elastomer in bottle brush form obtained in example 18 has higher mechanical strength due to higher chitin content, although the monomer ratio is the same, compared with example 12.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A full-bio-based bottle brush-shaped thermoplastic elastomer is characterized in that: the structural formula is as follows:
wherein n is more than or equal to 50 and less than or equal to 200, m is more than or equal to 100 and less than or equal to 1000, l is more than or equal to 0 and less than or equal to 1000, R 1 Is composed of
Any one of the groups;
R 2 comprises the following steps:
R 3 comprises the following steps:
any one or more of the groups in (a).
2. The process for the preparation of a biobased bottle brush thermoplastic elastomer according to claim 1, characterized in that: the method comprises the following steps:
(1) adding a chitin macromolecular chain transfer agent, a reaction monomer A, a reaction monomer B and an initiator into a reaction bottle with a mixed solvent;
(2) removing water and air in the reaction bottle, reacting at 60-100 ℃, and collecting and drying a product after the reaction is finished;
the structural formula of the chitin macromolecular chain transfer agent is as follows:
3. the method of preparing a biobased bottle brush thermoplastic elastomer according to claim 2, wherein: the method for preparing the full-bio-based bottle brush-shaped thermoplastic elastomer specifically comprises the following steps:
(1) adding 1-10 parts by weight of chitin macromolecular chain transfer agent, 250-5200 parts by weight of reaction monomer A, 0-700 parts by weight of reaction monomer B and 0.015-0.3 part by weight of initiator into a reaction bottle containing 445-7500 parts by weight of mixed solvent;
(2) and (3) removing water and air in the reaction flask, reacting at 60-100 ℃, and collecting and drying the product after the reaction is finished.
4. The method of preparing a biobased bottle brush thermoplastic elastomer according to claim 2, wherein: the reaction monomer A is as follows:
5. The method of preparing a fully bio-based bottle brush thermoplastic elastomer according to claim 2, wherein: the reaction monomer B is as follows:
any one or more groups of (a).
6. The method of preparing a biobased bottle brush thermoplastic elastomer according to claim 2, wherein: the mixed solvent in the step (1) is prepared from N, N-dimethylformamide and 1, 4-dioxane according to the volume ratio of 6: 4.
7. The method of preparing a biobased bottle brush thermoplastic elastomer according to claim 2, wherein: and (2) performing freezing-vacuum-melting circulation on the reaction bottle, reacting for 12-48h at 60-100 ℃, then putting the reaction bottle into a precipitator for precipitation and collection, and then putting the collected product into a vacuum dryer at 50-80 ℃.
8. The method of preparing a biobased bottle brush thermoplastic elastomer according to claim 2, wherein: the preparation method of the chitin macromolecular chain transfer agent in the step (1) comprises the following steps:
(a) mixing 1-10 parts by weight of chitin and 40-600 parts by weight of 1-allyl-3-methylimidazole bromide ionic liquid until the chitin is completely dissolved in the 1-allyl-3-methylimidazole bromide ionic liquid to form a solution;
(b) placing the solution in the step (1) in an ice-water bath, slowly dropwise adding 50-600 parts by weight of bromopropionyl bromide, removing the ice-water bath after dropwise adding is finished, reacting at room temperature, and after the reaction is finished, precipitating, washing and drying to obtain a chitin initiator;
(c) dissolving 1-10 parts by weight of chitin initiator in 25-240 parts by weight of dimethyl sulfoxide, dissolving 0.2-3 parts by weight of benzyl mercaptan, 0.4-6 parts by weight of carbon disulfide and 0.2-3 parts by weight of triethylamine in 6-60 parts by weight of dimethyl sulfoxide, mixing the two mixed solutions, reacting at 40 ℃, and after the reaction is finished, precipitating, washing and drying to obtain the chitin chain transfer agent.
9. The method of preparing a biobased bottle brush thermoplastic elastomer according to claim 8, wherein: the reaction in the step (b) is carried out for 48 to 72 hours at room temperature, then the precipitation is carried out in pure water, and the vacuum drying is carried out at 50 to 80 ℃ overnight.
10. The method of preparing a biobased bottle brush thermoplastic elastomer according to claim 8, wherein: and (c) mixing the two mixed solutions in the step (c), reacting at 40 ℃ for 12-24h, precipitating in pure water, washing, and drying in vacuum at 50-80 ℃ overnight.
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| CN104356318A (en) * | 2014-11-10 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Lignin-based starlike thermoplastic elastomer and preparation method thereof |
| WO2020006721A1 (en) * | 2018-07-04 | 2020-01-09 | 南通纺织丝绸产业技术研究院 | High-grafting density cyclic comb shaped polymer and preparation method therefor |
| CN111187385A (en) * | 2019-08-26 | 2020-05-22 | 中国科学技术大学 | Cellulose-based bottle-brush-shaped thermoplastic elastomer and preparation method thereof |
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| CN104356318A (en) * | 2014-11-10 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Lignin-based starlike thermoplastic elastomer and preparation method thereof |
| WO2020006721A1 (en) * | 2018-07-04 | 2020-01-09 | 南通纺织丝绸产业技术研究院 | High-grafting density cyclic comb shaped polymer and preparation method therefor |
| CN111187385A (en) * | 2019-08-26 | 2020-05-22 | 中国科学技术大学 | Cellulose-based bottle-brush-shaped thermoplastic elastomer and preparation method thereof |
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