CN115417970B - Transparent rosin-based self-repairing polyurethane elastomer and synthetic method and application thereof - Google Patents
Transparent rosin-based self-repairing polyurethane elastomer and synthetic method and application thereof Download PDFInfo
- Publication number
- CN115417970B CN115417970B CN202211150940.XA CN202211150940A CN115417970B CN 115417970 B CN115417970 B CN 115417970B CN 202211150940 A CN202211150940 A CN 202211150940A CN 115417970 B CN115417970 B CN 115417970B
- Authority
- CN
- China
- Prior art keywords
- rosin
- acrylic
- polyurethane elastomer
- acid
- pimaric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 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 title claims abstract description 53
- 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 title claims abstract description 53
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 31
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 claims abstract description 58
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 claims abstract description 53
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 51
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 acrylic pimaric acid allyl ester Chemical class 0.000 claims abstract description 21
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 10
- 239000011344 liquid material Substances 0.000 claims abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims abstract description 3
- 125000002252 acyl group Chemical group 0.000 claims abstract description 3
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000004132 cross linking Methods 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 20
- 239000012046 mixed solvent Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 238000002390 rotary evaporation Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 14
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 7
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000009489 vacuum treatment Methods 0.000 claims 1
- 150000003141 primary amines Chemical class 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- FPODCVUTIPDRTE-UHFFFAOYSA-N bis(prop-2-enyl) hexanedioate Chemical compound C=CCOC(=O)CCCCC(=O)OCC=C FPODCVUTIPDRTE-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical group CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- MWEKYZJBAPKADE-UHFFFAOYSA-N 1-(diisocyanatomethyl)-4-methylbenzene Chemical compound CC1=CC=C(C(N=C=O)N=C=O)C=C1 MWEKYZJBAPKADE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KXMTXZACPVCDMH-UHFFFAOYSA-N methyl 4-[5-(hydroxymethyl)-7-methoxy-1,3-benzodioxol-4-yl]-7-methoxy-1,3-benzodioxole-5-carboxylate Chemical compound COC(=O)C1=CC(OC)=C2OCOC2=C1C1=C2OCOC2=C(OC)C=C1CO KXMTXZACPVCDMH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
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Abstract
A transparent rosin-based self-repairing polyurethane elastomer, a synthetic method and application thereof, wherein after D-A addition reaction of rosin and acrylic acid, acrylic pimaric acid is obtained through separation and purification; performing acyl chlorination reaction on the purified acrylic pimaric acid and oxalyl chloride to obtain acrylic pimaric acid chloride; adding an acid binding agent triethylamine and hydroxyethyl acrylate into acrylic pimaric acid chloride to obtain acrylic pimaric acid allyl ester; allyl acrylate and a catalyst react with primary amine to obtain rosin-based diamine; and fully reacting the synthesized rosin-based diamine, the chain extender blocked by hydroxyl and isocyanate, adding glycerol for crosslinking and blocking, and curing the liquid material to obtain the rosin-based self-repairing polyurethane elastomer. The invention simultaneously considers the mechanical property, the self-repairing property and the transparency of the polyurethane elastomer, can be applied to invisible vehicle clothing and screen protective films, and has wide practical application range.
Description
Technical Field
The invention belongs to the technical field of polymer material preparation, and particularly relates to a transparent rosin-based self-repairing polyurethane elastomer, and a synthetic method and application thereof.
Background
The material is stimulated by the external environment for a long time in the use process, a certain degree of damage (such as scratches and microcracks) is inevitably generated, and the long-time accumulation of the damage which is difficult to detect leads to the degradation of the material performance, the potential safety hazard initiation, the service life reduction and even the damage failure. Under the inspired of self-healing of injured tissues of animals, people prepare self-repairing materials with the capability of self-detecting and repairing injuries by designing dynamic reversible chemical bonds in a polymer molecular network. Currently, self-healing polymeric materials based on dynamic covalent reversible bonds (e.g., oxime-urethane bonds, disulfide bonds, B-O bonds, imine bonds, diels-Alder reactions, etc.) and reversible non-covalent interactions (hydrogen bonds, metal-coordination bonds, host-guest interactions, etc.) have been reported, but their self-healing process requires external conditions of stimulation, such as high temperature, high pressure, light or other media, which greatly limit their use in real life.
Bao et al prepared a PU elastomer with notch insensitivity and high stretchability self-repairing, and the fracture sample healed for 48 hours at room temperature can be stretched to 1500% again, and the self-healing efficiency is as high as 78%. However, the application of the non-ideal tensile strength (< 2 MPa) is greatly limited by .(Kang J,Son D,Wang G J N,et al.Tough and water-insensitive self-healing elastomer for robust electronic skin[J].Advanced Materials,2018,30(13):1706846). Chinese patent application CN 114940740A, which discloses a high-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions, reversible covalent bonds (borate and oxime urethane bonds) are introduced into polyurethane molecular chains, finally metal salts and oxime urethane bonds are added to form coordination actions, multiple dynamic actions are introduced into polyurethane, the structure of a polymer molecular chain is reasonably regulated and controlled, the mechanical strength can reach 15.3+/-0.7 MPa, meanwhile, the high elongation at break (1232+/-68%) is maintained, and the self-repairing efficiency of more than 90% can be achieved after repairing for 24 hours under the room temperature condition, but the self-repairing efficiency still needs to be further improved to meet the requirements of practical application.
According to the invention, rosin-derived acrylic pimaric acid with a rigid three-dimensional polycyclic structure is used as a raw material, and a dynamic hard microphase is constructed by combining graded association hydrogen bonds, so that the contradiction between segment fluidity and mechanical property stability required by self-repairing performance is balanced, and the self-repairing PU elastomer with excellent mechanical property is prepared. The amorphous loose hard domains give the elastomer high permeability under the influence of rosin ring steric hindrance, giving it feasibility for application in the fields of invisible car covers and screen protection films.
At present, most of development of self-repairing polymer materials is based on petrochemical-based chemicals as raw materials, and the preparation of the self-repairing polymer materials by using natural renewable and nontoxic biomass raw materials has important significance in view of environmental protection, and meanwhile, the development of the biomass-based self-repairing polymer materials not only accords with the concept of sustainable development, but also improves the added value of related biomass resources and expands the utilization way of the biomass resources.
Disclosure of Invention
The technical problems to be solved are as follows: the invention provides a transparent rosin-based self-repairing polyurethane elastomer, a synthesis method and application thereof, which take biomass resources as raw materials to prepare a biomass-based polymer which is high in strength, toughness, transparency, self-repairing and reprocessable.
The technical scheme is as follows: the preparation method of the transparent rosin-based self-repairing polyurethane elastomer comprises the following steps: (1) After the addition reaction of rosin and acrylic acid through D-A, the acrylic pimaric acid is obtained through separation and purification; (2) Performing acyl chlorination reaction on the purified acrylic pimaric acid and oxalyl chloride, wherein the molar ratio of carboxyl to acyl chloride is 1 (2-2.5), so as to obtain acrylic pimaric acid acyl chloride; adding an acid binding agent triethylamine and hydroxyethyl acrylate into acrylic acid chloride, wherein the molar ratio of the acrylic acid chloride to the hydroxyethyl acrylate to the triethylamine is 1 (2-3), performing vacuum filtration on the obtained product, washing the product with deionized water until the pH value is neutral, collecting an organic phase, removing water with anhydrous magnesium sulfate, performing vacuum filtration, and performing rotary evaporation to obtain acrylic acid allyl ester; (3) The allyl acrylate, the catalyst and primary amine react for 24 to 48 hours at the temperature of 20 to 50 ℃, the mol ratio of the allyl acrylate to the amine is 1 (1 to 2), unreacted amine is removed by rotary evaporation, deionized water is used for washing until the pH value is neutral, an organic phase is collected, anhydrous magnesium sulfate is used for removing water, suction filtration is carried out, and rosin-based diamine can be obtained after rotary evaporation; (4) And fully reacting the synthesized rosin-based diamine, the hydroxyl-terminated chain extender and isocyanate, adding glycerol to crosslink and terminate, wherein the mole ratio of the rosin-based diamine, the hydroxyl-terminated chain extender, the glycerol to the isocyanate is (3.6-7.2): (8.4-4.8): 2:15, and curing the liquid material to obtain the rosin-based self-repairing polyurethane elastomer.
Preferably, the process of step (1) is as follows: heating rosin and hydroquinone of polymerization inhibitor to 160 ℃ under the protection of nitrogen, dropwise adding acrylic acid, heating to 230 ℃, continuously reacting for 3.5 hours, and cooling to obtain crude product of acrylic pimaric acid, wherein the mass ratio of rosin to acrylic acid to hydroquinone is 50:12:3; dissolving the crushed product in a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5, heating the mixed solvent to reflux the solvent for 3 hours, cooling the mixed solvent to room temperature, continuously stirring the mixed solvent for 3 hours, carrying out vacuum filtration, and recrystallizing the mixed solvent in ethyl acetate to obtain the purified acrylic pimaric acid.
Preferably, the process of step (2) is as follows: dissolving the purified acrylic pimaric acid in tetrahydrofuran, adding oxalyl chloride, wherein the molar ratio of carboxyl of the acrylic pimaric acid to acyl chloride of the oxalyl chloride is 1:2.2, and reacting for 3-6 hours at 20-60 ℃ to obtain acrylic pimaric acid chloride; adding an acid binding agent triethylamine and hydroxyethyl acrylate into acrylic pimaric acid chloride, wherein the molar ratio of the acrylic pimaric acid chloride to the hydroxyethyl acrylate to the triethylamine is 1:3:2.5, and reacting for 4-6 hours at the temperature of 0-20 ℃; and (3) removing triethylamine hydrochloride by suction filtration, washing with deionized water until the pH value is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, suction filtering, and rotary steaming to obtain allyl acrylate.
Preferably, the molar ratio of allyl groups to amine groups of the allyl acrylate in step (3) is 1:1.5.
Preferably, the amine in step (3) is tert-butylamine, methylamine, ethylamine, ammonia, aniline, furfuryl amine or cyclopentylamine; the catalyst is N-bromosuccinimide (NBS), sodium methoxide, anhydrous ferric chloride or cation exchange resin.
Preferably, the process of step (4) is as follows: mixing and stirring the synthesized rosin-based diamine, hydroxyl-terminated chain extender and isocyanate in N, N-dimethylacetamide, reacting for 2-4 hours at 60-80 ℃, adding glycerol and continuously reacting for 4-6 hours at 60-80 ℃.
Preferably, the solidification in step (4) is carried out by pouring the liquid material into a polytetrafluoroethylene or polypropylene (PP) mold, placing the mold in an oven at 80 ℃ for 24 hours, and then vacuum-treating the mold at 80-120 ℃ for 12 hours to sufficiently remove the solvent.
Preferably, the chain extender in the step (4) is polytetrahydrofuran, polyethylene glycol, polyether amine, polycarbonate diol or polypropylene glycol, and the molecular weight is 800-2000; the isocyanate is hexamethylene diisocyanate, isophorone diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyl methylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-1, 4-methylbenzylene diisocyanate, p-1, 4-methylbenzylene diisocyanate or dimer acid diisocyanate.
The transparent rosin-based self-repairing polyurethane elastomer prepared by the synthetic method.
The transparent rosin-based self-repairing polyurethane elastomer is applied to the preparation of invisible car covers and screen protection films.
The beneficial effects are that: the invention simultaneously considers the mechanical property, self-repairing property and transparency of the polyurethane elastomer, the tensile strength of the prepared self-repairing elastomer can reach 34.8MPa, the elongation at break is 1121.77 percent, the repairing efficiency for 24h under the room temperature condition can reach 87.65 percent, and the self-repairing elastomer can be applied to invisible car covers and screen protection films and has wide practical application range.
Drawings
FIG. 1 is a synthetic route diagram of an acrylic pimaric acid based di-tert-butylamine chain extender of example 1 of the present invention;
FIG. 2 is a structural formula of the chain extender synthesized in comparative example 1 and comparative example 2 according to the present invention;
FIG. 3 is an infrared spectrum of purified acrylic acid, allyl esters of acrylic acid.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the embodiments described are only some embodiments of the present invention, but not all embodiments.
Example 1
(1) Purification of pimaric acid: 120.00g of industrial acrylic rosin is taken, crushed and then added into a 1000mL four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 600mL of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 is measured and added into the four-necked flask, the mixture is heated to the solvent for reflux reaction for 3 hours, the mixture is cooled to room temperature and then stirred for 3 hours, the mixture is subjected to vacuum suction filtration, and a small amount of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 is used for washing for 3 times, so that crude product of the pimaric acid is obtained. Adding 40.00g of crude product of the pimaric acid into a 250mL four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, measuring 150mL of ethyl acetate, adding the mixture into the four-necked flask, heating the mixture until the solvent flows back, filtering the mixture while the solution is hot after the pimaric acid is completely dissolved, standing the filtrate, and after the pimaric acid is fully crystallized, carrying out vacuum suction filtration on the filtrate, and washing the filtrate with a small amount of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 for 3 times to obtain the purified pimaric acid.
(2) Synthesis of allyl acrylate pimarate: pimaric acid (50 g,0.1336 mol) was dissolved in ethyl acetate, oxalyl chloride (37.01 g,0.3 mol) was added, the pimaric acid chloride was obtained by reacting at 50℃for 5 hours, then triethylamine (30.4 g,0.3 mol) as an acid-binding agent and hydroxyethyl acrylate (38.3 g,0.33 mmol) were added to the pimaric acid chloride, the reaction was carried out at 20℃for 2 to 5 hours, the precipitate was filtered off, the solvent layer was collected, washed with water, and water was removed. Suction filtering and rotary steaming to obtain the allyl acrylate.
(3) Synthesis of a propenoic acid group di-tert-butylamine chain extender: allyl acrylate (50 g,0.088 mol), anhydrous ferric chloride (0.12 g,0.2 wt.%) and tertiary butylamine (9.65 g,0.132 mol) are reacted for 24-48 hours at 20-50 ℃, unreacted amine is removed by rotary evaporation, deionized water is used for washing until the pH value is neutral, an organic phase is collected, anhydrous magnesium sulfate is used for removing water, suction filtration is carried out, and the propylene pimaric acid group di-tertiary butylamine chain extender can be obtained after rotary evaporation;
(4) Preparation of a high-performance transparent rosin-based self-repairing polyurethane elastomer: the synthesized propylene pimaric acid group di-tert-butylamine chain extender, polytetrahydrofuran with 1000 molecular weight and isophorone diisocyanate are mixed according to the mole ratio of 6:6:15 in N, N-dimethylacetamide, and reacting at 60-80 ℃ for 2-4 h. Adding glycerol to react for 4-6 hours at 60-80 ℃, wherein the mol ratio of the glycerol to the isophorone diisocyanate is 2:15. after the reaction, the liquid material was poured into a polypropylene (PP) mold and placed in an 80 ℃ oven for 24 hours. Vacuum processing is carried out for 12 hours at 80-120 ℃ to fully remove the solvent.
Example 2
(1) Purification of pimaric acid: 120.00g of industrial acrylic rosin is taken, crushed and then added into a 1000mL four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 600mL of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 is measured and added into the four-necked flask, the mixture is heated to the solvent for reflux reaction for 3 hours, the mixture is cooled to room temperature and then stirred for 3 hours, the mixture is subjected to vacuum suction filtration, and a small amount of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 is used for washing for 3 times, so that crude product of the pimaric acid is obtained. Adding 40.00g of crude product of the pimaric acid into a 250mL four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, measuring 150mL of ethyl acetate, adding the mixture into the four-necked flask, heating the mixture until the solvent flows back, filtering the mixture while the solution is hot after the pimaric acid is completely dissolved, standing the filtrate, and after the pimaric acid is fully crystallized, carrying out vacuum suction filtration on the filtrate, and washing the filtrate with a small amount of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 for 3 times to obtain the purified pimaric acid.
(2) Synthesis of allyl acrylate pimarate: pimaric acid (50 g,0.1336 mol) was dissolved in ethyl acetate, oxalyl chloride (37.01 g,0.3 mol) was added, the pimaric acid chloride was obtained by reacting at 50℃for 5 hours, then triethylamine (30.4 g,0.3 mol) as an acid-binding agent and hydroxyethyl acrylate (38.3 g,0.33 mmol) were added to the pimaric acid chloride, the reaction was carried out at 20℃for 2 to 5 hours, the precipitate was filtered off, the solvent layer was collected, washed with water, and water was removed. Suction filtering and rotary steaming to obtain the allyl acrylate.
(3) Synthesis of an acrylic pimaric acid-based diethylamine chain extender: allyl acrylate (50 g,0.088 mol), anhydrous ferric chloride (0.11 g,0.2 wt.%) and ethylamine (5.95 g,0.132 mol) are reacted for 24-48 hours at 20-50 ℃, unreacted amine is removed by rotary evaporation, deionized water is used for washing until the pH value is neutral, an organic phase is collected, anhydrous magnesium sulfate is used for removing water, suction filtration is carried out, and the acrylic pimaric acid-based diethylamine chain extender can be obtained after rotary evaporation;
(4) Preparation of a high-performance transparent rosin-based self-repairing polyurethane elastomer: the synthesized propylene pimaric acid-based diethylamine chain extender, polytetrahydrofuran with 1000 molecular weight and isophorone diisocyanate are mixed according to the mole ratio of 6:6:15 in N, N-dimethylacetamide, and reacting at 60-80 ℃ for 2-4 h. Adding glycerol to react for 4-6 hours at 60-80 ℃, wherein the mol ratio of the glycerol to the isophorone diisocyanate is 2:15. after the reaction, the liquid material was poured into a polypropylene (PP) mold and placed in an 80 ℃ oven for 24 hours. Vacuum processing is carried out for 12 hours at 80-120 ℃ to fully remove the solvent.
Example 3
(1) Purification of pimaric acid: 120.00g of industrial acrylic rosin is taken, crushed and then added into a 1000mL four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 600mL of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 is measured and added into the four-necked flask, the mixture is heated to the solvent for reflux reaction for 3 hours, the mixture is cooled to room temperature and then stirred for 3 hours, the mixture is subjected to vacuum suction filtration, and a small amount of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 is used for washing for 3 times, so that crude product of the pimaric acid is obtained. Adding 40.00g of crude product of the pimaric acid into a 250mL four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, measuring 150mL of ethyl acetate, adding the mixture into the four-necked flask, heating the mixture until the solvent flows back, filtering the mixture while the solution is hot after the pimaric acid is completely dissolved, standing the filtrate, and after the pimaric acid is fully crystallized, carrying out vacuum suction filtration on the filtrate, and washing the filtrate with a small amount of petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5 for 3 times to obtain the purified pimaric acid.
(2) Synthesis of allyl acrylate pimarate: pimaric acid (50 g,0.1336 mol) was dissolved in ethyl acetate, oxalyl chloride (37.01 g,0.3 mol) was added, the pimaric acid chloride was obtained by reacting at 50℃for 5 hours, then triethylamine (30.4 g,0.3 mol) as an acid-binding agent and hydroxyethyl acrylate (38.3 g,0.33 mmol) were added to the pimaric acid chloride, the reaction was carried out at 20℃for 2 to 5 hours, the precipitate was filtered off, the solvent layer was collected, washed with water, and water was removed. Suction filtering and rotary steaming to obtain the allyl acrylate.
(3) Synthesis of a propenoic acid group di-tert-butylamine chain extender: allyl acrylate (50 g,0.088 mol), anhydrous ferric chloride (0.12 g,0.2 wt.%) and tertiary butylamine (9.65 g,0.132 mol) are reacted for 24-48 hours at 20-50 ℃, unreacted amine is removed by rotary evaporation, deionized water is used for washing until the pH value is neutral, an organic phase is collected, anhydrous magnesium sulfate is used for removing water, suction filtration is carried out, and the propylene pimaric acid group di-tertiary butylamine chain extender can be obtained after rotary evaporation;
(4) Preparation of a high-performance transparent rosin-based self-repairing polyurethane elastomer: the synthesized propylene pimaric acid-based diethylamine chain extender, polytetrahydrofuran with 1000 molecular weight and hexamethylene diisocyanate are mixed according to the mole ratio of 6:6:15 in N, N-dimethylacetamide, and reacting at 60-80 ℃ for 2-4 h. Adding glycerol to react for 4-6 hours at 60-80 ℃, wherein the mol ratio of the glycerol to the isophorone diisocyanate is 2:15. after the reaction, the liquid material was poured into a polypropylene (PP) mold and placed in an 80 ℃ oven for 24 hours. Vacuum processing is carried out for 12 hours at 80-120 ℃ to fully remove the solvent.
Comparative example 1
(1) Synthesis of allyl adipate: adipic acid (20 g,0.1369 mol) was dissolved in ethyl acetate, oxalyl chloride (37.01 g,0.3 mol) was added, the reaction was carried out at 50℃for 5 hours to give adipic acid chloride, then the acid-binding agent triethylamine (30.4 g,0.3 mol) and hydroxyethyl acrylate (38.3 g,0.33 mmol) were added to the reaction product of the first step, the reaction was carried out at 20℃for 2 to 5 hours, the precipitate was filtered off, and the solvent layer was collected, washed with water, and dehydrated. Suction filtering and rotary steaming to obtain allyl adipate.
(2) Synthesis of adipic acid-based di-tert-butylamine chain extender: allyl adipate (50 g,0.135 mol), anhydrous ferric chloride (0.13 g,0.2 wt.%) and tertiary butylamine (14.82 g,0.203 mol) are reacted for 24-48 hours at 20-50 ℃, unreacted amine is removed by rotary evaporation, deionized water is used for washing until the pH value is neutral, an organic phase is collected, anhydrous magnesium sulfate is used for removing water, suction filtration is carried out, and the adipic acid di-tertiary butylamine chain extender can be obtained after rotary evaporation;
(3) Preparation of a high-performance transparent rosin-based self-repairing polyurethane elastomer: the synthesized adipic acid di-tert-butylamine chain extender, polytetrahydrofuran with 1000 molecular weight and isophorone diisocyanate are mixed according to the mole ratio of 6:6:15 in N, N-dimethylacetamide, and reacting at 60-80 ℃ for 2-4 h. Adding glycerol to react for 4-6 hours at 60-80 ℃, wherein the mol ratio of the glycerol to the isophorone diisocyanate is 2:15. after the reaction, the liquid material was poured into a polypropylene (PP) mold and placed in an 80 ℃ oven for 24 hours. Vacuum processing is carried out for 12 hours at 80-120 ℃ to fully remove the solvent.
Comparative example 2
(1) Synthesis of allyl dicyclohexylate: bicyclol (20 g,0.1 mol) is dissolved in ethyl acetate, 0.2wt.% hydroquinone inhibitor and acid-binding agent triethylamine (16.2 g,0.16 mol) are added, acryloyl chloride (37.01 g,0.15 mol) is added dropwise, the reaction is carried out at room temperature for 5 hours to obtain allyl dicyclohexyl, the precipitate is filtered, water washing is carried out, a solvent layer is collected, and the allyl dicyclohexyl is obtained by recrystallization in petroleum ether.
(2) Synthesis of dicyclohexyl di-tert-butylamine chain extender: allyl dicyclohexylate (50 g,0.163 mol), anhydrous ferric chloride (0.14 g,0.2 wt.%) and tertiary butylamine (17.9 g,0.245 mol) are reacted for 24-48 hours at 20-50 ℃, unreacted amine is removed by rotary evaporation, deionized water is used for washing until the pH value is neutral, an organic phase is collected, anhydrous magnesium sulfate is used for removing water, suction filtration and rotary evaporation are carried out, and then the dicyclohexylate di-tertiary butylamine chain extender can be obtained;
(3) Preparation of a high-performance transparent rosin-based self-repairing polyurethane elastomer: the synthesized dicyclohexyl di-tert-butylamine chain extender, polytetrahydrofuran with 1000 molecular weight and isophorone diisocyanate are mixed according to the mole ratio of 6:6:15 in N, N-dimethylacetamide, and reacting at 60-80 ℃ for 2-4 h. Adding glycerol to react for 4-6 hours at 60-80 ℃, wherein the mol ratio of the glycerol to the isophorone diisocyanate is 2:15. after the reaction, the liquid material was poured into a polypropylene (PP) mold and placed in an 80 ℃ oven for 24 hours. Vacuum processing is carried out for 12 hours at 80-120 ℃ to fully remove the solvent.
Example 1 is a high performance transparent rosin-based self-healing polyurethane elastomer prepared according to the present invention. Example 2 changes the amine group from t-butylamine to ethylamine and example 3 changes the isophorone diisocyanate containing an irregular six-membered ring to a linear hexamethylene diisocyanate. Comparative example 1 is a rosin ring structure replaced with linear hexane, and comparative example 2 is a rosin ring structure replaced with dicyclohexyl. By comparative example 1, comparative example 2, comparative example 3, it was confirmed that the strong rigidity of the rosin ring leads to enhancement of the mechanical properties of the elastomer. By comparing example 1, example 2 and example 3, it is demonstrated that the loose hard domains are advantageous to maintain dynamic characteristics, thereby achieving higher self-healing efficiency.
Table 1 mechanical properties and self-healing efficiency of each example and comparative example
The above examples are examples of the present invention for preparing the high performance transparent rosin-based self-repairing polyurethane elastomer, but the present invention is not limited to the above examples, and the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be equivalent substitution, which is included in the scope of the present invention.
Claims (10)
1. The preparation method of the transparent rosin-based self-repairing polyurethane elastomer is characterized by comprising the following steps of: (1) After the addition reaction of rosin and acrylic acid through D-A, the acrylic pimaric acid is obtained through separation and purification; (2) Performing acyl chlorination reaction on the purified acrylic pimaric acid and oxalyl chloride, wherein the molar ratio of carboxyl to acyl chloride is 1 (2-2.5), so as to obtain acrylic pimaric acid acyl chloride; adding an acid binding agent triethylamine and hydroxyethyl acrylate into acrylic acid chloride, wherein the molar ratio of the acrylic acid chloride to the hydroxyethyl acrylate to the triethylamine is 1 (2-3), performing vacuum filtration on the obtained product, washing the product with deionized water until the pH value is neutral, collecting an organic phase, removing water with anhydrous magnesium sulfate, performing vacuum filtration, and performing rotary evaporation to obtain acrylic acid allyl ester; (3) The allyl acrylate, the catalyst and tertiary butylamine react for 24-48 hours at 20-50 ℃, the mol ratio of allyl to amino of the allyl acrylate is 1 (1-2), unreacted amine is removed by rotary evaporation, deionized water is used for washing until the pH value is neutral, an organic phase is collected, anhydrous magnesium sulfate is used for removing water, suction filtration is carried out, and rosin-based diamine can be obtained after rotary evaporation; (4) And fully reacting the synthesized rosin-based diamine, the hydroxyl-terminated chain extender and the isophorone diisocyanate, adding glycerol for crosslinking and capping, wherein the mole ratio of the rosin-based diamine, the hydroxyl-terminated chain extender, the glycerol and the isocyanate is (3.6-7.2): (8.4-4.8): 2:15, and curing the liquid material to obtain the rosin-based self-repairing polyurethane elastomer.
2. The method for preparing the transparent rosin-based self-repairing polyurethane elastomer according to claim 1, wherein the process of step (1) is as follows: heating rosin and hydroquinone of polymerization inhibitor to 160 ℃ under the protection of nitrogen, dropwise adding acrylic acid, heating to 230 ℃, continuously reacting for 3.5 h, cooling to obtain crude product of acrylic pimaric acid, wherein the mass ratio of rosin to acrylic acid to hydroquinone is 50:12:3; dissolving the crushed product in a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 95:5, heating the mixed solvent to reflux the solvent to 3h, cooling the mixed solvent to room temperature, continuously stirring the mixed solvent to 3h, carrying out vacuum filtration under reduced pressure, and recrystallizing the mixed solvent in ethyl acetate to obtain the purified acrylic pimaric acid.
3. The method for preparing the transparent rosin-based self-repairing polyurethane elastomer according to claim 1, wherein the process of the step (2) is as follows: dissolving the purified acrylic pimaric acid in tetrahydrofuran, adding oxalyl chloride, wherein the molar ratio of carboxyl of the acrylic pimaric acid to acyl chloride of the oxalyl chloride is 1:2.2, and reacting for 3-6 hours at 20-60 ℃ to obtain acrylic pimaric acid chloride; adding an acid binding agent triethylamine and hydroxyethyl acrylate into acrylic pimaric acid chloride, wherein the molar ratio of the acrylic pimaric acid chloride to the hydroxyethyl acrylate to the triethylamine is 1:3:2.5, and reacting for 4-6 hours at the temperature of 0-20 ℃; and (3) removing triethylamine hydrochloride by suction filtration, washing with deionized water until the pH value is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, suction filtering, and rotary steaming to obtain allyl acrylate.
4. The method for producing a transparent rosin-based self-repairing polyurethane elastomer according to claim 1, wherein the molar ratio of allyl groups to amine groups of the allyl acrylate in the step (3) is 1:1.5.
5. The method for preparing the transparent rosin-based self-repairing polyurethane elastomer according to claim 1, wherein the catalyst in the step (3) is N-bromosuccinimide (NBS), sodium methoxide, anhydrous ferric chloride or cation exchange resin.
6. The method for preparing the transparent rosin-based self-repairing polyurethane elastomer according to claim 1, wherein the process of the step (4) is as follows: and mixing and stirring the synthesized rosin-based diamine, the hydroxyl-terminated chain extender and the isophorone diisocyanate in N, N-dimethylacetamide, reacting for 2-4 hours at 60-80 ℃, adding glycerol and continuously reacting for 4-6 hours at 60-80 ℃.
7. The method for preparing the transparent rosin-based self-repairing polyurethane elastomer according to claim 1, wherein in the step (4), the liquid material is poured into a polytetrafluoroethylene (polytetrafluoroethylene) or polypropylene (PP) mold, and the mold is placed in an 80 ℃ oven 24h, and then is subjected to vacuum treatment at 80-120 ℃ for 12h to sufficiently remove the solvent.
8. The method for preparing the transparent rosin-based self-repairing polyurethane elastomer according to claim 1, wherein the chain extender in the step (4) is polytetrahydrofuran, polyethylene glycol, polyether amine, polycarbonate diol or polypropylene glycol, and the molecular weight is 800-2000.
9. A transparent rosin-based self-healing polyurethane elastomer prepared by the method of any one of claims 1 to 8.
10. Use of the transparent rosin-based self-healing polyurethane elastomer of claim 9 in the preparation of invisible car covers and screen protection films.
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