CN112794983B - Preparation method of visible light cured self-repairing fluorine-containing polyurethane resin - Google Patents
Preparation method of visible light cured self-repairing fluorine-containing polyurethane resin Download PDFInfo
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- CN112794983B CN112794983B CN202110002691.9A CN202110002691A CN112794983B CN 112794983 B CN112794983 B CN 112794983B CN 202110002691 A CN202110002691 A CN 202110002691A CN 112794983 B CN112794983 B CN 112794983B
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- fluorine
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- visible light
- acid
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 121
- 239000011737 fluorine Substances 0.000 title claims abstract description 121
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002383 tung oil Substances 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 20
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 238000000016 photochemical curing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 229920002635 polyurethane Polymers 0.000 claims description 49
- 239000004814 polyurethane Substances 0.000 claims description 49
- 238000005406 washing Methods 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 36
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical class CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 229920005862 polyol Polymers 0.000 claims description 17
- 150000003077 polyols Chemical class 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010907 mechanical stirring Methods 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 12
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- -1 methylenebis-4, 1-phenylene Chemical group 0.000 claims description 5
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 claims description 4
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 claims description 4
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 claims 2
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 claims 1
- RPCVQJIIXZQJSO-UHFFFAOYSA-N CC(C)(C(C1=CC=C(CC(C=C2)=CC=C2C(C(C)(C)OC(C(F)(F)F)=O)=O)C=C1)=O)OC(C(F)(F)F)=O Chemical compound CC(C)(C(C1=CC=C(CC(C=C2)=CC=C2C(C(C)(C)OC(C(F)(F)F)=O)=O)C=C1)=O)OC(C(F)(F)F)=O RPCVQJIIXZQJSO-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 230000021523 carboxylation Effects 0.000 abstract description 9
- 238000006473 carboxylation reaction Methods 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000413 hydrolysate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 34
- 238000001723 curing Methods 0.000 description 19
- CUXYLFPMQMFGPL-WPOADVJFSA-N (9Z,11E,13E)-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C/CCCCCCCC(O)=O CUXYLFPMQMFGPL-WPOADVJFSA-N 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 11
- 238000005979 thermal decomposition reaction Methods 0.000 description 11
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- AQXYVFBSOOBBQV-UHFFFAOYSA-N 1-amino-4-hydroxyanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2N AQXYVFBSOOBBQV-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 235000001484 Trigonella foenum graecum Nutrition 0.000 description 1
- 244000250129 Trigonella foenum graecum Species 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NVJMGQMXNBBZIU-UHFFFAOYSA-N dibutyltin;1-dodecylsulfanyldodecane Chemical compound CCCC[Sn]CCCC.CCCCCCCCCCCCSCCCCCCCCCCCC NVJMGQMXNBBZIU-UHFFFAOYSA-N 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 235000001019 trigonella foenum-graecum Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6828—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Abstract
The invention belongs to the field of photocuring bio-based intelligent materials, and particularly relates to a preparation method of visible light-cured self-repairing fluorine-containing polyurethane resin. Firstly, dichloromethane, a double-active functional group photoinitiator, a weak alkaline acid-binding agent and trifluoroacetyl chloride are reacted in a nitrogen protection device to prepare a fluorine-containing photoinitiator; performing double carboxylation treatment on the tung oil acid which is a hydrolysate of the triglyceride of the tung oil acid, and finally preparing the self-repairing fluorine-containing polyurethane resin cured under the visible light condition under the synergistic action of a dihydroxyl fluorine-containing monomer, a fluorine-containing photoinitiator and diisocyanate. The polyurethane resin overcomes the defects of high brittleness, easy breakage and poor high temperature resistance of the traditional light-cured resin, is cured by utilizing visible light which is friendly to human bodies, has a self-repairing function, can prolong the service life of the material, enhances the weather resistance and the high temperature resistance, and has renewable monomer sources and good application prospect.
Description
Technical Field
The invention belongs to the field of photocuring bio-based intelligent materials, and particularly relates to a preparation method of visible light-cured self-repairing fluorine-containing polyurethane resin.
Background
The photocuring resin has the advantages of high curing speed, extremely small organic volatile, low cost and simple and convenient operation, and is widely applied to the fields of 3D printing, artificial bones, special coatings, adhesives and the like. Conventional photocurable resins are cured by ultraviolet light, require specialized equipment to generate the ultraviolet radiation, which is expensive and harmful to the human body.
Because of excellent properties such as friction resistance, low temperature resistance, microphase separation, controllable hardness and the like, the polyurethane is widely applied to the fields of aviation, railways, automobile parts, coatings and the like. However, polyurethanes are poor in high temperature resistance, their tensile strength and tear strength are markedly reduced with increasing temperature, and their mechanical properties are still lacking. In addition, due to the small molecular structure of the chain extender, the chain extender is easy to photodegrade and thermally degrade, and has short service life. In order to make up for the defects of the polyurethane material, F is introduced into the polyurethane to enhance the high-temperature resistance of the polyurethane material, greatly reduce the surface energy, super-hydrophobicity, oleophobicity and the like, improve the solvent resistance of the polyurethane material, prolong the service life of the polyurethane material, and can be applied to automobile and airplane fuel tanks and protective coatings in extreme environments, thereby expanding the application range of the polyurethane material.
In recent years, there have been many studies for introducing F into polyurethane materials. For example: fluorine is introduced into the waterborne polyurethane by Lifengyan, Zuoyijie and the like, so that the water resistance of the perfluoroalkyl ethyl acrylate adhesive film and the lubricity of a fracture surface of the perfluoroalkyl ethyl acrylate adhesive film are improved; the fluorine atoms are introduced into the fluorine-containing contact antibacterial polyurethane, such as the fenugreek, the Penkemei and the like, so that the antibacterial activity of the polyurethane is greatly improved, and meanwhile, the fluorine element can also effectively inhibit the pollution on the surface of the polyurethane and prolong the antibacterial service life of the polyurethane. The traditional fluorine-containing polyurethane resin is cured by moisture or bi-component isocyanate, uses a large amount of solvent, has low curing efficiency, is not environment-friendly and harmful to health, does not have a self-repairing function, and has short service life and poor mechanical property.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of visible light curing self-repairing fluorine-containing polyurethane resin, which solves the defects of high brittleness and poor low temperature resistance of polyurethane resin. The fluorine-containing polyurethane is cured by using visible light which is friendly to human bodies, and has high curing efficiency, good mechanical properties of materials and good high temperature resistance. And the material has a self-repairing function, so that the service life of the material is prolonged. Meanwhile, the tung oil acid triglyceride bio-based raw material is adopted in the preparation process, the source is renewable, the waste material can be partially degraded, and the method is green and environment-friendly and can be widely applied to the fields of coating, decoration, packaging and the like.
The invention provides a preparation method of visible light curing self-repairing fluorine-containing polyurethane resin, which comprises the following steps:
(1) preparation of fluorine-containing photoinitiator: adding dichloromethane into a three-neck flask provided with a nitrogen protection and magnetic stirring device, dissolving a double-active functional group photoinitiator and a weakly alkaline acid-binding agent into dichloromethane, magnetically stirring at room temperature to uniformly mix the initiators and the weakly alkaline acid-binding agent, reacting for 2 hours, rapidly cooling, slowly adding dichloroethane and trifluoroacetyl chloride into a reaction container in sequence under the condition of ice-water bath, controlling the reaction temperature to be 5 ℃, reacting for 6 hours, filtering, washing, and drying to obtain the fluorine-containing photoinitiator.
Wherein the double-active functional group photoinitiator comprises 1, 1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ], 1-amino-4-hydroxyanthraquinone, 1, 4-diamino-9, 10-anthracenedione, 1, 5-diaminoanthraquinone and the like.
The weak alkaline acid-binding agent is one or a mixture of more of triethylamine, n-butylamine, pyridine and trimethylamine.
In the preparation method, the molar ratio of the materials is as follows: dual active functional group photoinitiator: the ratio of trifluoroacetyl chloride is 1: 2-1: 3; dichloromethane: weakly alkaline acid-binding agent: dichloroethane is 1:1 (1-4);
the structural formula of the prepared fluorine-containing photoinitiator is shown as follows:
fluorine-containing photoinitiator 1:
fluorine-containing photoinitiator 2:
fluorine-containing photoinitiator 3:
fluorine-containing photoinitiator 4:
f is introduced into the photoinitiator, so that the fusion of the photoinitiator and the resin is improved, and the resin is cured under visible light. Meanwhile, the high temperature resistance, the tensile strength and the elongation at break of the polyurethane material are enhanced.
(2) Preparation of dicarboxy unsaturated eleostearic acid: adding tung oil acid triglyceride and 10% sodium hydroxide solution into a round-bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with 0.5mol/L sulfuric acid, washing with saturated NaCl solution for three times, and drying to obtain unsaturated tung oil acid. Adding unsaturated eleostearic acid into a three-neck flask, dropwise adding THF, dropwise adding n-BuLi under an ice water bath to react for about 0.5h, then adding CuCl, heating to room temperature, stirring to react for 1.5h at the stirring speed of 150r/min, removing THF under reduced pressure, adding a pyridine solution dissolved with 4-iodoanisole into a reaction bottle by using a syringe, heating to 100 ℃ to react for 48h, adding a pyridine solution dissolved with potassium permanganate, reacting for 3h, extracting with 1mol/LHCl aqueous solution, drying by spinning and drying, and finally separating a product by using column chromatography (petroleum ether: ethyl acetate: 35:1), thereby obtaining the dicarboxy unsaturated eleostearic acid.
In the preparation method, the molar ratio of the materials is as follows: sulfuric acid: 2: 1-6: 1 of sodium hydroxide; unsaturated eleostearic acid: THF: n-BuLi: 1, (4-6) and (2-3) of CuCl; unsaturated eleostearic acid: 4-iodoanisole: and (3.6-4) potassium permanganate being 1: 2.
The eleostearic acid is subjected to double carboxylation treatment, so that a dihydroxyl fluorine-containing monomer is conveniently introduced for polymerization in the subsequent process, and a large amount of fluorine elements are introduced, so that the material has a self-repairing function. Meanwhile, the bio-based tung oil monomer is contained, so that the bio-based tung oil monomer can be partially degraded and is more environment-friendly.
(3) Adding a dihydroxyl fluorine-containing monomer and dicarboxy unsaturated eleostearic acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2 hours at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, then adding a catalyst, a fluorine-containing photoinitiator and diisocyanate, cooling to 75 ℃, and reacting for 5 hours. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane.
The used dihydroxy fluorine-containing monomer is as follows:
wherein the values of x and y are 20-60;
the main chain and the side chain of the dihydroxyl fluorine-containing monomer contain a large amount of fluorine elements, and the interior of the dihydroxyl fluorine-containing monomer contains a large amount of fluorine-containing hydrogen bonds. At a lower temperature, the fluorine-containing hydrogen bond has better activity, and is beneficial to realizing the self-repairing function, which is not possessed by other fluorine-containing monomers.
Wherein the molar ratio of the materials is as follows: bis-hydroxy fluoromonomer: dicarboxy unsaturated eleostearic acid: fluorine-containing photoinitiator: the diisocyanate is 2-5: 1:1: 2.
The diisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-Xylylene Diisocyanate (XDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane-4, 4' -diisocyanate (HMDI).
The catalyst is one or a mixture of more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, dibutyltin dilaurate, stannous octoate, dibutyltin didodecyl sulfide and dibutyltin diacetate, and the dosage of the catalyst is 1-3% of the total mass of the dihydroxyl fluorine-containing monomer and the dicarboxy unsaturated eleostearic acid.
The self-repairing fluorine-containing polyurethane resin prepared by the invention has the following structure:
wherein the values of a, b and c are 1-20.
Has the advantages that: according to the invention, through the synergistic effect of the fluorine-containing photoinitiator and the tung oil-based fluorine-containing polyurethane, the tensile strength and the heat resistance of the polyurethane material can be enhanced, and the polyurethane material can be cured under visible light which is friendly to human bodies, and is closer to the actual use environment of the material. In addition, the polyurethane can realize partial degradation by introducing the tung oil acid triglyceride bio-based monomer. Meanwhile, a large amount of fluorine elements are introduced into the polyurethane, so that a large amount of fluorine-containing hydrogen bonds exist in the structure of the polyurethane, and the polyurethane has a good self-repairing function.
The visible light curing self-repairing fluorine-containing polyurethane resin prepared by the invention is cured under visible light, the visible light source is solar irradiation, and the visible light curing self-repairing fluorine-containing polyurethane resin is renewable energy, is inexhaustible and is friendly to human bodies. In addition, the polyol monomer raw material in the fluorine-containing polyurethane is tung oil which is a renewable biological source and can be partially degraded. The product can be applied to the fields of coating, decoration, packaging, adhesives, polymer battery electrolytes and the like, the service life and the safety coefficient of the material are improved, and the environmental pollution of plastics is reduced.
Drawings
FIG. 1 is an infrared spectrum of a fluorine-containing photoinitiator 1 to 4 prepared in example;
FIG. 2 is an IR spectrum of a photocurable fluorine-containing polyurethane as a final product obtained in example 1;
fig. 3 is a picture of the self-healing of the material prepared in example 1 at different temperatures.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
20mL of dichloromethane were added to a three-necked flask equipped with a nitrogen blanket and a magnetic stirrer, and 0.01mol of 1, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ] and 0.01mol of triethylamine were dissolved in dichloromethane and mixed by magnetic stirring at room temperature. After reacting for 2h, rapidly cooling, slowly adding 15mL of dichloroethane and 0.02mol of trifluoroacetyl chloride into the reaction vessel in sequence under the ice-water bath condition, controlling the reaction temperature at 5 ℃, reacting for 6h, filtering, washing and drying to obtain the fluorine-containing photoinitiator, wherein the yield is 86%.
Adding 0.01mol of elaeostearic acid triglyceride and 0.03mol of 10% sodium hydroxide solution into a 100mL round-bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with excessive 0.5mol/L sulfuric acid, washing with 30mL of saturated NaCl solution for three times, and drying to obtain unsaturated elaeostearic acid (wherein the molar ratio of the sulfuric acid to the sodium hydroxide is 2: 1).
Adding 0.01mol of unsaturated eleostearic acid into a three-neck flask, dropwise adding 30mL of Hydrogen Fluoride (HF), dropwise adding 14mmol of n-BuLi under an ice water bath for reacting for about 0.5h, then adding 16mmol of CuCl, heating to room temperature, stirring for reacting for 1.5h at the stirring speed of 150r/min, removing THF under reduced pressure, adding 25mL of pyridine solution dissolved with 14mmol of 4-iodoanisole into a reaction bottle by using a syringe, heating to 100 ℃ for reacting for 48h, adding 25mL of pyridine solution dissolved with 7mmol of potassium permanganate, reacting for 3h, extracting with 1mol/LHCl aqueous solution, evaporating to dryness, and finally separating the product by using column chromatography (petroleum ether: ethyl acetate: 35:1) to obtain the dicarboxy unsaturated eleostearic acid.
0.02mol of dihydroxyl fluorine-containing monomer
Adding 0.01mol of dicarboxyl unsaturated eleostearic acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2h at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, then adding 1 mass percent of catalyst N, N-dimethyl cyclohexylamine, 0.01mol of fluorine-containing photoinitiator and 0.02mol of toluene diisocyanate, cooling to 75 ℃, and reacting for 5 h. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane. The product has a yield of 89% and a molecular weight of 55200.
FIG. 2 Infrared analysis shows 822cm in the product-1And 1220cm-1Of (a) is-CF3and-CF2The appearance of characteristic peaks, indicating the successful introduction of F into the polyurethane system; at 1710cm-1The characteristic peak near the carboxyl group disappeared at 2900cm-1Left and right occurrence of-CH3Characteristic peak at 1450cm-1And 3000cm-1Left and right-CH2Characteristic peak of (D), 1600cm-1Characteristic peak of left and right benzene rings, 1735cm-1C ═ O stretching vibration, 1540cm-1And 3300cm-1The bending vibration of N-H indicates that the visible light curing self-repairing fluorine-containing polyurethane resin is successfully synthesized.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to enable the product samples to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is 60min when the temperature is measured to be 40 ℃; the time is 30min at 60 ℃; the time is 16min at 80 ℃. The tensile strength was 12.14MPa, and the elongation at break was 590%. Irradiation with visible lightAfter that, the complete curing time was 180 s. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 295 ℃ and the char yield at 400 ℃ in an air atmosphere was 61%.
Example 2
30mL of methylene chloride was placed in a three-necked flask equipped with a nitrogen blanket and a magnetic stirrer, and 0.02mol of 1, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ] and 0.02mol of n-butylamine were dissolved in methylene chloride and mixed by magnetic stirring at room temperature. After reacting for 2h, rapidly cooling, slowly adding 20mL of dichloroethane and 0.04mol of trifluoroacetyl chloride into the reaction vessel in sequence under the ice-water bath condition, controlling the reaction temperature at 5 ℃, filtering after reacting for 6h, washing and drying to obtain the fluorine-containing photoinitiator, wherein the yield is 88%.
Adding 0.02mol of elaeostearic acid triglyceride and 0.06mol of 10% sodium hydroxide solution into a 100mL round bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with excessive 0.5mol/L sulfuric acid, washing with 30mL of saturated NaCl solution for three times, and drying to obtain unsaturated elaeostearic acid (wherein the molar ratio of the sulfuric acid to the sodium hydroxide is 3: 1).
Unsaturated eleostearic acid was subjected to a double carboxylation treatment (same as in example 1).
0.06mol of dihydroxyl fluorine-containing monomer
Adding 0.02mol of dicarboxyl unsaturated eleostearic acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2h at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, then adding 1 mass percent of catalyst N, N-dimethylbenzylamine, 0.02mol of fluorine-containing photoinitiator and 0.04mol of diphenylmethane diisocyanate, cooling to 75 ℃, and reacting for 5 h. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane. The product was obtained in 84% yield and had a molecular weight of 55423.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to ensure that the product samples have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is measured to be 40 DEG C55 min; at 60 deg.C, the time is 27 min; the time is 15min at 80 ℃. The tensile strength was 12.02MPa, and the elongation at break was 572%. The complete curing time was 175s after irradiation with visible light. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 297 ℃ and the char yield was 63% at 400 ℃ in an air atmosphere.
Example 3
35mL of methylene chloride was placed in a three-necked flask equipped with a nitrogen blanket and a magnetic stirrer, and 0.03mol of 1, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ] and 0.03mol of trimethylamine were dissolved in methylene chloride and mixed by magnetic stirring at room temperature. After reacting for 2h, rapidly cooling, slowly adding 25mL of dichloroethane and 0.06mol of trifluoroacetyl chloride into the reaction vessel in turn under the ice-water bath condition, controlling the reaction temperature at 5 ℃, filtering after reacting for 6h, washing and drying to obtain the fluorine-containing photoinitiator, wherein the yield is 89%.
Adding 0.03mol of elaeostearic acid triglyceride and 0.09mol of 10% sodium hydroxide solution into a 100mL round-bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with excessive 0.5mol/L sulfuric acid, washing with 30mL of saturated NaCl solution for three times, and drying to obtain unsaturated elaeostearic acid (wherein the molar ratio of the sulfuric acid to the sodium hydroxide is 4: 1).
Unsaturated eleostearic acid was subjected to a double carboxylation treatment (same as in example 1).
0.12mol of dihydroxyl fluorine-containing monomer
Adding the hydroxyl-terminated tung oil-based fluorine-containing polyol and 0.03mol of dicarboxyl unsaturated tung oil acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2h at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, then adding a catalyst dibutyltin dilaurate with the mass fraction of 1%, 0.03mol of fluorine-containing photoinitiator and 0.06mol of hexamethylene diisocyanate, cooling to 75 ℃, and reacting for 5 h. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane. The product yield was 86% and the molecular weight was 56024.
In order to verify the self-repairing performance of the polyurethane, three are takenProduct samples are divided to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is 50min when the temperature is measured to be 40 ℃; the time is 23min at 60 ℃; the time is 12min at 80 ℃. The tensile strength was 12.60MPa, and the elongation at break was 582%. The complete curing time after irradiation with visible light was 171 s. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature is 299 ℃, and the carbon residue rate is 65% at 400 ℃ in the air atmosphere.
Example 4
35mL of methylene chloride was placed in a three-necked flask equipped with a nitrogen blanket and a magnetic stirrer, and 0.03mol of 1, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ] and 0.03mol of pyridine were dissolved in methylene chloride and mixed by magnetic stirring at room temperature. After reacting for 2h, rapidly cooling, slowly adding 25mL of dichloroethane and 0.09mol of trifluoroacetyl chloride into the reaction vessel in sequence under the ice-water bath condition, controlling the reaction temperature at 5 ℃, reacting for 6h, filtering, washing and drying to obtain the fluorine-containing photoinitiator, wherein the yield is 87%.
Adding 0.03mol of elaeostearic acid triglyceride and 0.09mol of 10% sodium hydroxide solution into a 100mL round-bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with excessive 0.5mol/L sulfuric acid, washing with 30mL of saturated NaCl solution for three times, and drying to obtain unsaturated elaeostearic acid (wherein the molar ratio of the sulfuric acid to the sodium hydroxide is 6: 1).
Unsaturated eleostearic acid was subjected to a double carboxylation treatment (same as in example 1).
0.15mol of dihydroxyl fluorine-containing monomer
Adding the hydroxyl-terminated tung oil-based fluorine-containing polyol and 0.03mol of dicarboxyl unsaturated tung oil acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2h at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, then adding a catalyst dibutyltin diacetate with the mass fraction of 1%, 0.03mol of fluorine-containing photoinitiator and 0.06mol of isophorone diisocyanate, cooling to 75 ℃, and reacting for 5 h. Washing and drying to obtain the tung oil-based fluorine-containing polymerAn urethane. The product was obtained in 84% yield and had a molecular weight of 57300.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to enable the product samples to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is 46min when the temperature is measured to be 40 ℃; at 60 deg.C, the time is 20 min; the time is 10min at 80 ℃. The tensile strength was 12.56MPa, and the elongation at break was 591%. The complete curing time was 169s after irradiation with visible light. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 301 ℃ and the char yield at 400 ℃ in an air atmosphere was 66%.
Example 5
30mL of methylene chloride was placed in a three-necked flask equipped with a nitrogen blanket and a magnetic stirrer, and 0.02mol of 1-amino-4-hydroxyanthraquinone and 0.02mol of trimethylamine were dissolved in methylene chloride and mixed by magnetic stirring at room temperature. After reacting for 2h, rapidly cooling, slowly adding 20mL of dichloroethane and 0.04mol of trifluoroacetyl chloride into the reaction vessel in sequence under the ice-water bath condition, controlling the reaction temperature at 5 ℃, filtering after reacting for 6h, washing and drying to obtain the fluorine-containing photoinitiator, wherein the yield is 85%.
Adding 0.02mol of elaeostearic acid triglyceride and 0.06mol of 10% sodium hydroxide solution into a 100mL round bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with excessive 0.5mol/L sulfuric acid, washing the oil layer with 30mL of saturated NaCl solution for three times, and drying to obtain unsaturated elaeostearic acid (wherein the molar ratio of the sulfuric acid to the sodium hydroxide is 3: 1).
Unsaturated eleostearic acid was subjected to a double carboxylation treatment (same as in example 1).
0.06mol of dihydroxyl fluorine-containing monomer
Adding the hydroxyl-terminated tung oil-based fluorine-containing polyol and 0.02mol of dicarboxyl unsaturated eleostearic acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2 hours at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, and then adding 2 mass percent of catalyst N, N-dimethylbenzylamine, 0.02mol of fluorine-containing photoinitiator and 0.04mol of hexa-methylbenzylamineAnd (3) cooling the methylene diisocyanate to 70 ℃, and reacting for 5 hours. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane. The product was obtained in 86% yield and had a molecular weight of 56426.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to enable the product samples to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is 60min when the temperature is measured to be 40 ℃; at 60 deg.C, the time is 36 min; the time is 21min at 80 ℃. The tensile strength was 12.24MPa, and the elongation at break was 570%. The complete curing time was 170s after irradiation with visible light. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 286 ℃ and the char yield was 62% at 400 ℃ in an air atmosphere.
Example 6
30mL of dichloromethane was added to a three-necked flask equipped with a nitrogen blanket and a magnetic stirrer, and 0.02mol of 1, 4-diamino-9, 10-anthracenedione and 0.02mol of triethylamine were dissolved in dichloromethane and mixed by magnetic stirring at room temperature. After reacting for 2h, rapidly cooling, slowly adding 20mL of dichloroethane and 0.04mol of trifluoroacetyl chloride into the reaction vessel in sequence under the ice-water bath condition, controlling the reaction temperature at 5 ℃, filtering after reacting for 6h, washing and drying to obtain the fluorine-containing photoinitiator, wherein the yield is 86%.
Adding 0.02mol of elaeostearic acid triglyceride and 0.06mol of 10% sodium hydroxide solution into a 100mL round bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with excessive 0.5mol/L sulfuric acid, washing with 30mL of saturated NaCl solution for three times, and drying to obtain unsaturated elaeostearic acid (wherein the molar ratio of the sulfuric acid to the sodium hydroxide is 3: 1).
Unsaturated eleostearic acid was subjected to a double carboxylation treatment (same as in example 1).
0.06mol of dihydroxyl fluorine-containing monomer
Adding 0.02mol of dicarboxyl unsaturated eleostearic acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2h at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol,then adding 3 percent of catalyst N, N-dimethylbenzylamine, 0.02mol of fluorine-containing photoinitiator and 0.04mol of isophorone diisocyanate, cooling to 65 ℃, and reacting for 5 hours. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane. The product was obtained in 86% yield and had a molecular weight of 57100.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to enable the product samples to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is 57min when the temperature is measured to be 40 ℃; the time is 31min at 60 ℃; the time is 19min at 80 ℃. The tensile strength was 12.53MPa, and the elongation at break was 575%. The complete curing time after irradiation with visible light was 171 s. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 282 ℃ and the char yield at 400 ℃ in an air atmosphere was 61%.
Example 7
35mL of methylene chloride was placed in a three-necked flask equipped with a nitrogen blanket and a magnetic stirrer, and 0.03mol of 1, 4-diamino-9, 10-anthracenedione and 0.03mol of n-butylamine were dissolved in methylene chloride and mixed by magnetic stirring at room temperature. After reacting for 2h, rapidly cooling, slowly adding 25mL of dichloroethane and 0.06mol of trifluoroacetyl chloride into the reaction vessel in turn under the ice-water bath condition, controlling the reaction temperature at 5 ℃, filtering after reacting for 6h, washing and drying to obtain the fluorine-containing photoinitiator, wherein the yield is 88%.
Adding 0.03mol of elaeostearic acid triglyceride and 0.09mol of 10% sodium hydroxide solution into a 100mL round-bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with excessive 0.5mol/L sulfuric acid, washing with 30mL of saturated NaCl solution for three times, and drying to obtain unsaturated elaeostearic acid (wherein the molar ratio of the sulfuric acid to the sodium hydroxide is 6: 1).
Unsaturated eleostearic acid was subjected to a double carboxylation treatment (same as in example 1).
0.15mol of dihydroxyl fluorine-containing monomer
Adding 0.03mol of dicarboxyl unsaturated eleostearic acid into the mixture,Reacting for 2 hours at 85 ℃ in a three-neck flask with a mechanical stirring device to generate tung oil-based fluorine-containing polyol with a hydroxyl end capping, then adding a catalyst of dibutyltin diacetate with the mass fraction of 2%, 0.03mol of fluorine-containing photoinitiator and 0.06mol of isophorone diisocyanate, cooling to 70 ℃, and reacting for 5 hours. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane. The product was obtained in 87% yield and had a molecular weight of 57459.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to enable the product samples to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is 45min when the temperature is measured to be 40 ℃; at 60 deg.C, the time is 20 min; the time is 10min at 80 ℃. The tensile strength is 12.70MPa, and the elongation at break is 593%. The complete curing time was 175s after irradiation with visible light. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 290 ℃ and the char yield was 62% at 400 ℃ in an air atmosphere.
Example 8
35mL of methylene chloride was placed in a three-necked flask equipped with a nitrogen blanket and a magnetic stirrer, and 0.03mol of 1, 5-diaminoanthraquinone and 0.03mol of triethylamine were dissolved in methylene chloride and mixed by magnetic stirring at room temperature. After reacting for 2h, rapidly cooling, slowly adding 25mL of dichloroethane and 0.09mol of trifluoroacetyl chloride into the reaction vessel in sequence under the ice-water bath condition, controlling the reaction temperature at 5 ℃, reacting for 6h, filtering, washing and drying to obtain the fluorine-containing photoinitiator, wherein the yield is 87%.
Adding 0.03mol of elaeostearic acid triglyceride and 0.09mol of 10% sodium hydroxide solution into a 100mL round-bottom flask, heating to fully react for 50min, separating liquid, washing an oil layer with excessive 0.5mol/L sulfuric acid, washing with 30mL of saturated NaCl solution for three times, and drying to obtain unsaturated elaeostearic acid (wherein the molar ratio of the sulfuric acid to the sodium hydroxide is 6: 1).
Unsaturated eleostearic acid was subjected to a double carboxylation treatment (same as in example 1).
0.15mol of dihydroxyl fluorine-containing monomer
Adding the hydroxyl-terminated tung oil-based fluorine-containing polyol and 0.03mol of dicarboxyl unsaturated tung oil acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2h at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, then adding a catalyst dibutyltin diacetate with the mass fraction of 3%, 0.03mol of fluorine-containing photoinitiator and 0.06mol of isophorone diisocyanate, cooling to 70 ℃, and reacting for 5 h. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane. The product was 89% yield and had a molecular weight of 58026.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to enable the product samples to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is 43min when the temperature is measured to be 40 ℃; at 60 deg.C, the time is 19 min; the time is 10min at 80 ℃. The tensile strength is 12.81MPa, and the elongation at break is 597%. The complete curing time was 172s after irradiation with visible light. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 293 ℃ and the char yield at 400 ℃ in an air atmosphere was 64%.
Comparative example 1
The preparation method of dicarboxy unsaturated eleostearic acid is the same as that of example 1.
0.02mol of dihydroxyl fluorine-containing monomer
Adding 0.01mol of dicarboxyl unsaturated eleostearic acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2h at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, then adding 1 mass percent of catalyst N, N-dimethyl cyclohexylamine, 0.01mol of conventional photoinitiator 2-hydroxy-2-methyl-1-phenyl propane-1-ketone and 0.02mol of toluene diisocyanate, cooling to 75 ℃, and reacting for 5 h. And washing and drying to obtain the tung oil-based fluorine-containing polyurethane. The yield of the product was 82% and the molecular weight was 50240.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to ensure that the product samples have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is measured when the temperature is 40 DEG CIs 72 min; the time is 46min at 60 ℃; the time is 25min at 80 ℃. The tensile strength was 6.51MPa and the elongation at break was 772%. After irradiation with visible light, no curing can take place. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 270 ℃ and the char yield was 54% at 400 ℃ in an air atmosphere.
Comparative example 2
The same procedure as in example 1 was followed for the preparation of the fluorine-containing photoinitiator and biscarboxyl unsaturated tung oil acid.
Adding 0.02mol of polytetrahydrofuran glycol and 0.01mol of dicarboxy unsaturated eleostearic acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2h at 85 ℃ to generate hydroxyl-terminated eleostearic oil-based polyol, then adding 1% by mass of catalyst N, N-dimethylcyclohexylamine, 0.01mol of fluorine-containing photoinitiator and 0.02mol of toluene diisocyanate, cooling to 75 ℃, and reacting for 5 h. And washing and drying to obtain the tung oil-based polyurethane. The product was obtained in 84% yield and had a molecular weight of 49520.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to enable the product samples to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is 28 hours when the temperature is measured to be 40 ℃; the time is 26h at 60 ℃; the time is 20h at 80 ℃. The tensile strength was 9.27MPa, and the elongation at break was 621%. After irradiation with visible light, the complete curing time was 2 h. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 231 ℃ and the char yield was 34% at 400 ℃ in an air atmosphere.
Comparative example 3
The preparation of the fluorine-containing photoinitiator was the same as in example 1.
0.02mol of dihydroxyl fluorine-containing monomer
1 percent of catalyst N, N-dimethylcyclohexylamine, 0.01mol of fluorine-containing photoinitiator and 0.04mol of toluene diisocyanate are added into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, and the reaction is carried out for 5 hours at 75 ℃. Washing and drying to obtain the fluorine-containing polyurethaneAnd (3) an ester. The yield of the product was 82% and the molecular weight was 40216.
In order to verify the self-repairing performance of the polyurethane, three product samples are taken to enable the product samples to have consistent scratch length and depth, the samples are respectively placed under different temperature conditions, and the self-repairing time is measured to be 16h at 40 ℃; the time is 12h at 60 ℃; the time is 10h at 80 ℃. The tensile strength was 6.21MPa and the elongation at break was 698%. After irradiation with visible light, no curing can take place. In the heat resistance test, the mass loss was 5% (T)5) The thermal decomposition temperature was 252 ℃ and the char yield at 400 ℃ in an air atmosphere was 46%.
The self-repairing efficiency of the fluorinated polyurethane resin obtained in each example of the present invention and the comparative example at different temperatures is shown in table 1:
TABLE 1
Claims (7)
1. A preparation method of visible light cured self-repairing fluorine-containing polyurethane resin is characterized in that: the preparation method comprises the following steps:
(1) synthesis of fluorine-containing photoinitiator
Adding dichloromethane into a three-neck flask provided with a nitrogen protection and magnetic stirring device, dissolving a double-active functional group photoinitiator and a weakly alkaline acid-binding agent into dichloromethane, magnetically stirring at room temperature to uniformly mix the initiators and the weakly alkaline acid-binding agent, reacting for 2 hours, rapidly cooling, slowly adding dichloroethane and trifluoroacetyl chloride into a reaction container in sequence under the condition of ice-water bath, controlling the reaction temperature to be 5 ℃, reacting for 6 hours, filtering, washing, and drying to obtain a fluorine-containing photoinitiator;
the dual-active functional group photoinitiator comprises the following components: 1, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone]Having a structural formula of
；
1-amino group-4-hydroxyanthraquinone, the structural formula of which is
(ii) a 1, 4-diamino-9, 10-anthracenedione with the structural formula
Or 1, 5-diaminoanthraquinone, the structural formula of which is
(ii) a The molar ratio of the double-active functional group photoinitiator to trifluoroacetyl chloride is 1: 2-1: 3;
(2) preparation of dicarboxy unsaturated eleostearic acid
Adding tung oil acid triglyceride and 10% sodium hydroxide solution into a round-bottom flask provided with a nitrogen protection and mechanical stirring device, heating to fully react for 50min, separating liquid, washing an oil layer with 0.5mol/L sulfuric acid, washing with saturated NaCl solution for three times, and drying to obtain unsaturated tung oil acid; adding unsaturated eleostearic acid into a three-neck flask, dropwise adding THF, dropwise adding n-BuLi under an ice water bath for reaction for 0.5h, then adding CuCl, heating to room temperature, stirring for reaction for 1.5h at the stirring speed of 150r/min, removing THF under reduced pressure, adding a pyridine solution dissolved with 4-iodoanisole into a reaction bottle by using an injector, heating to 100 ℃ for reaction for 48h, adding a pyridine solution dissolved with potassium permanganate, reacting for 3h, extracting by using 1mol/L HCl aqueous solution, and after rotary drying and evaporation, finally separating petroleum ether by using column chromatography, wherein ethyl acetate =35:1, so as to obtain dicarboxy unsaturated eleostearic acid;
(3) preparation of photocured fluorine-containing polyurethane
Adding a dihydroxyl fluorine-containing monomer and dicarboxy unsaturated eleostearic acid into a three-neck flask which is filled with nitrogen and is provided with a mechanical stirring device, reacting for 2 hours at 85 ℃ to generate hydroxyl-terminated tung oil-based fluorine-containing polyol, then adding a catalyst, a fluorine-containing photoinitiator and diisocyanate, cooling to 75 ℃, reacting for 5 hours, washing and drying to obtain photocuring fluorine-containing polyurethane;
the structural formula of the dihydroxy fluorine-containing monomer is as follows:
wherein the values of x and y are 20-60.
2. The process for producing a visible light-curable self-repairing fluorine-containing polyurethane resin according to claim 1, wherein: the weak alkaline acid-binding agent in the step (1) is one or a mixture of more of triethylamine, n-butylamine, pyridine and trimethylamine.
3. The process for producing a visible light-curable self-repairing fluorine-containing polyurethane resin according to claim 1, wherein: the structural formula of the fluorine-containing photoinitiator in the step (1) is as follows:
(methylenebis (4, 1-phenylene)) bis (2-methyl-1-oxopropane-1, 2-diyl) bis (2, 2, 2-trifluoroacetic acid)
9, 10-dioxo-4- (2, 2, 2-trifluoroacetylamino) -9, 10-dihydroanthracen-1-yl 2,2, 2-trifluoroacetate salt
N, N' - (9, 10-dioxo-9, 10-dihydroanthracene-1, 4-dialkyl) bis (2, 2, 2-trifluoroacetamide)
N, N' - (9, 10-dioxo-9, 10-dihydroanthracene-1, 5-dialkyl) bis (2, 2, 2-trifluoroacetamide).
4. The process for producing a visible light-curable self-repairing fluorine-containing polyurethane resin according to claim 1, wherein: the catalyst in the step (3) is one or a mixture of more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfide) and dibutyltin diacetate, and the dosage of the catalyst is 1-3% of the total mass of the dihydroxyl fluorine-containing monomer and the dicarboxy unsaturated eleostearic acid.
5. The process for producing a visible light-curable self-repairing fluorine-containing polyurethane resin according to claim 1, wherein: the diisocyanate in the step (3) is one or a mixture of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-Xylylene Diisocyanate (XDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane-4, 4' -diisocyanate (HMDI).
6. The process for producing a visible light-curable self-repairing fluorine-containing polyurethane resin according to claim 1, wherein: the molar ratio of the dihydroxyl fluorine-containing monomer, the dicarboxy unsaturated eleostearic acid, the fluorine-containing photoinitiator and the diisocyanate in the step (3) is as follows: 2-5: 1:1: 2.
7. A visible light-curable self-healing fluorine-containing polyurethane resin prepared according to the method of claim 1, wherein: the structural general formula of the self-repairing fluorine-containing polyurethane resin is as follows:
wherein the values of a, b and c are 1-20.
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| CN104231228A (en) * | 2014-08-14 | 2014-12-24 | 广东工业大学 | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin |
| CN105693981A (en) * | 2015-03-09 | 2016-06-22 | 河南省科学院高新技术研究中心 | Tung oil polyol based anionic polyurethane with post-crosslinking capacity and preparation method of anionic polyurethane |
| CN105860017A (en) * | 2016-04-12 | 2016-08-17 | 江南大学 | Bio-based photosensitive polyurethane resin, and self-repairing coating made of resin |
| CN110606931A (en) * | 2019-09-09 | 2019-12-24 | 南昌航空大学 | Preparation method of waterborne light-cured self-repairing polyurethane resin |
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| CN104231228A (en) * | 2014-08-14 | 2014-12-24 | 广东工业大学 | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin |
| CN105693981A (en) * | 2015-03-09 | 2016-06-22 | 河南省科学院高新技术研究中心 | Tung oil polyol based anionic polyurethane with post-crosslinking capacity and preparation method of anionic polyurethane |
| CN105860017A (en) * | 2016-04-12 | 2016-08-17 | 江南大学 | Bio-based photosensitive polyurethane resin, and self-repairing coating made of resin |
| CN110606931A (en) * | 2019-09-09 | 2019-12-24 | 南昌航空大学 | Preparation method of waterborne light-cured self-repairing polyurethane resin |
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