CN115286770B - Curing agent based on phenol-carbamate bond, and preparation method and application thereof - Google Patents
Curing agent based on phenol-carbamate bond, and preparation method and application thereof Download PDFInfo
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- CN115286770B CN115286770B CN202210962192.9A CN202210962192A CN115286770B CN 115286770 B CN115286770 B CN 115286770B CN 202210962192 A CN202210962192 A CN 202210962192A CN 115286770 B CN115286770 B CN 115286770B
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- urethane bond
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 9
- 150000003944 halohydrins Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 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 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- -1 4,4' -diaminodiphenyl ketone Chemical class 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
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- 230000015572 biosynthetic process Effects 0.000 abstract description 7
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- 238000001723 curing Methods 0.000 description 62
- 239000000463 material Substances 0.000 description 20
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- 238000003776 cleavage reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
- 230000007017 scission Effects 0.000 description 6
- UVYBETTVKBAZFI-UHFFFAOYSA-N 4-(6-hydroxyhexoxy)phenol Chemical compound OCCCCCCOC1=CC=C(O)C=C1 UVYBETTVKBAZFI-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 238000009849 vacuum degassing Methods 0.000 description 4
- FCMCSZXRVWDVAW-UHFFFAOYSA-N 6-bromo-1-hexanol Chemical compound OCCCCCCBr FCMCSZXRVWDVAW-UHFFFAOYSA-N 0.000 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 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- GFUCMNMXYOVTDJ-UHFFFAOYSA-N 2,4-diamino-6-butan-2-ylphenol Chemical compound CCC(C)C1=CC(N)=CC(N)=C1O GFUCMNMXYOVTDJ-UHFFFAOYSA-N 0.000 description 1
- UVKAOWGONVXXGD-UHFFFAOYSA-N 4-(5-hydroxypentoxy)phenol Chemical compound OCCCCCOC1=CC=C(O)C=C1 UVKAOWGONVXXGD-UHFFFAOYSA-N 0.000 description 1
- WJVQJXVMLRGNGA-UHFFFAOYSA-N 5-bromopentan-1-ol Chemical compound OCCCCCBr WJVQJXVMLRGNGA-UHFFFAOYSA-N 0.000 description 1
- DCBJCKDOZLTTDW-UHFFFAOYSA-N 5-chloropentan-1-ol Chemical compound OCCCCCCl DCBJCKDOZLTTDW-UHFFFAOYSA-N 0.000 description 1
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 1
- HGXIDBQJLNZRSZ-UHFFFAOYSA-N CC(C=CC(NC(NC1=CC=C(CC(C=C2)=CC=C2N)C=C1)=O)=C1)=C1NC(NC1=CC=C(CC(C=C2)=CC=C2N)C=C1)=O Chemical compound CC(C=CC(NC(NC1=CC=C(CC(C=C2)=CC=C2N)C=C1)=O)=C1)=C1NC(NC1=CC=C(CC(C=C2)=CC=C2N)C=C1)=O HGXIDBQJLNZRSZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100035915 D site-binding protein Human genes 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 101000873522 Homo sapiens D site-binding protein Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000005891 transamination reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
Abstract
The invention belongs to the field of synthesis of curing agents of high polymer materials, and discloses a phenol-carbamate bond-based curing agent, and a preparation method and application thereof. The method comprises the following steps: under the atmosphere of nitrogen or inert gas, adding difunctional aromatic phenol and halohydrin into a solvent, stirring and dissolving, dropwise adding alkali liquor at 50-70 ℃ and dropwise adding and reacting for 8-14h; the obtained mixture of phenolic monomer and anhydrous solvent is dripped into difunctional isocyanate, organotin catalyst is added, magnetic stirring is carried out, and the reaction is carried out for 2-6h at 55-70 ℃ to obtain phenolic-carbamate bond. Cooling to 30-45 ℃, adding difunctional aromatic amine, and reacting for 3-6 hours at 30-45 ℃ to obtain a curing agent based on a phenol-carbamate bond; the curing agent based on the phenol-urethane bond can solve the defects of other dynamic covalent bonds, and the prepared epoxy resin has excellent mechanical property, thermal stability and self-healing property.
Description
Technical Field
The invention belongs to the field of synthesis of curing agents of high polymer materials, and particularly relates to a phenol-carbamate bond-based curing agent, and a preparation method and application thereof.
Background
Thermosetting resins have been widely used for bonding various metal and nonmetal materials, corrosion protection of metal surfaces, insulation of electronic devices, preparation of glass reinforced plastic/composite materials, and the like by virtue of their excellent mechanical properties, bonding properties, corrosion resistance, electrical insulation properties, and heat resistance. The composite material plays an important role in electronic, electric, mechanical manufacturing, chemical industry corrosion prevention, aerospace, ship transportation, chemical building materials, water conservancy and electric power and other industrial fields, becomes an indispensable basic material in various industrial fields, and has important value in daily living goods and high and new technical fields. Because of covalent cross-linking during the reaction, the thermosetting resin network is difficult to reconstruct even in a high temperature state, and the epoxy resin has great limitation in processing and remolding. The accumulation of large amounts of waste thermosetting resin materials now makes environmental and resource problems more serious, which makes it urgent to develop a thermosetting resin which is excellent in mechanical properties, self-repairable, recyclable and recyclable.
It has been found that the design and synthesis of suitable curing agents, incorporating reversible covalent structures into the polymer network, is critical in the development of repairable, recyclable thermosetting resins. Reversible covalent bonds reversibly cleave and recombine under external stimuli or specific conditions, causing the network to rearrange and impart dynamic properties such as circularity, shape memory or self-healing. At present, various reversible reaction and polymerization processes have been developed: diels-Alder reaction (CN 114213964 a), imine bond CN113512023 a), transesterification (CN 113248654B), disulfide bond (CN 112300356B), trans-amination (DOI: 10.1016/j.polymer.2018.04.076), trans-alkylation (DOI: 10.1039/c8gc02932 f), and siloxane balance (DOI: 10.1016/j.eurpolymj.2018.09.021), and the like. However, these methods all require catalysts or other specific conditions such as high temperature to allow reversible cleavage and recombination of the dynamic covalent bonds within the material.
Disclosure of Invention
In view of the shortcomings and drawbacks of the prior art, a primary object of the present invention is to provide a method for preparing a curing agent based on a phenol-urethane bond.
Another object of the present invention is to provide a phenol-urethane bond-based curing agent prepared by the above-mentioned preparation method.
It is a further object of the present invention to provide the use of the above-mentioned curing agent based on a phenol-urethane bond for curing an epoxy resin.
The aim of the invention is achieved by the following technical scheme:
a method for preparing a curing agent based on a phenol-urethane bond, comprising the steps of:
(1) Under the atmosphere of nitrogen or inert gas, adding difunctional aromatic phenol and halohydrin into a solvent, stirring and dissolving, dropwise adding alkali liquor at 50-70 ℃ for reaction for 8-14h, and obtaining phenolic monomers; wherein the mol ratio of the halohydrin, the difunctional aromatic phenol, the alkali liquor and the solvent is 1: (1-4): (0.5-2): (0.5-10);
(2) Dropwise adding a mixture of a phenolic monomer and an anhydrous solvent into difunctional isocyanate in a nitrogen or inert gas atmosphere, adding an organotin catalyst accounting for 0.5-1% of the total mass of reactants, magnetically stirring, and reacting for 2-6h at 55-70 ℃ to obtain a phenolic-carbamate bond;
cooling to 30-45 ℃, adding difunctional aromatic amine, and reacting for 3-6 hours at 30-45 ℃ to obtain a curing agent based on a phenol-carbamate bond; wherein the molar ratio of the phenolic monomer, the anhydrous solvent, the difunctional isocyanate and the difunctional aromatic amine is 1 (0.5-10): 1-4): 1-6;
the difunctional aromatic phenol in the step (1) is a difunctional aromatic phenol having a symmetrical structure, preferably hydroquinone, 4 '-dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfone, 4 '-dihydroxybenzophenone, 4' -dihydroxydiphenylpropane, and more preferably hydroquinone.
The alkali liquor in the step (1) is monobasic alkali liquor, including sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
The halohydrin in step (1) is a hydrocarbon having 4 to 8 straight-chain carbon atoms in the structure and having a chlorine atom or bromine atom at the end. Preferably, the halohydrin is at least one of 5-bromo-n-pentanol, 6-bromo-n-hexanol or 5-chloro-n-pentanol, 6-chloro-n-hexanol.
The solvent in the step (1) is at least one of tetrahydrofuran, absolute ethyl alcohol, water, toluene and acetone.
The structural formula of the difunctional aromatic amine in the step (2) is as follows:
wherein R is X Is an alkyl group having 1 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms, an ether group, a ketone group, a sulfone group, a thioether group or an amine group.
Preferably, the difunctional aromatic amine is one of 4,4' -diaminodiphenyl methane (DDM), 4' -diaminodiphenyl ether (ODA), 4' -diaminodiphenyl sulfone (DDS) or 4,4' -Diaminobenzophenone (DABP), more preferably 4,4' -diaminodiphenyl methane.
The structural formula of the difunctional isocyanate in the step (2) is as follows:
wherein R is y Is aryl or cycloparaffin or hydrocarbon group with linear carbon number of 4-10.
Preferably, the difunctional isocyanate is one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI) or diphenylmethane diisocyanate (MDI), more preferably toluene diisocyanate.
The anhydrous solvent in the step (2) is at least one of tetrahydrofuran, acetone, toluene, N-dimethylformamide and N, N-dimethylacetamide. The anhydrous solvent can prevent water molecules in the solvent from reacting with isocyanate, and the nitrogen or inert gas atmosphere can ensure an anhydrous environment.
The curing agent based on the phenol-urethane bond is prepared by the preparation method.
The application of the curing agent based on the phenol-urethane bond in epoxy resin and other thermosetting materials.
The curing agent based on the phenol-urethane bond prepared by the invention can be applied to curing of thermosetting resin, and can be used for preparing thermosetting resin materials with shape memory property, self-repairing property, reworkability and the like.
The curing agent based on the phenol-urethane bond is applied to the curing of epoxy resin and comprises the following steps: dissolving a curing agent containing a phenol-carbamate bond in an organic solvent, adding epoxy resin, and uniformly dispersing to obtain a mixed solution; and (3) carrying out vacuum defoamation on the mixed solution, transferring the mixed solution into a die, volatilizing the solvent in a blast oven at 40-80 ℃, and then carrying out heating and curing. The curing procedure is specifically as follows: curing for 2-4h at 90-130 ℃, 1-4h at 140-160 ℃ and 0.5-2h at 170-200 ℃ to obtain the self-repairing epoxy resin based on phenol-urethane bond dynamic covalent; wherein, the mole ratio of the curing agent to the epoxy resin is 1: (2-6).
The principle of the invention is as follows: the carbamate based on phenol formed by the reaction of phenolic hydroxyl groups and isocyanate groups automatically depolymerizes under high temperature conditions, and the temperature drops and repolymerizes. Reversible cleavage and recombination of the phenol-urethane bond can be achieved by adjusting the external temperature change. Through the transformation of the chemical bond in the use process of the material, the material has a reversible covalent network, and further has self-repairing performance and reworkability.
Compared with the prior art, the invention has the following advantages:
(1) The curing agent based on the phenol-urethane bond prepared by the invention can solve the defects of other dynamic covalent bonds, such as the need of a specific catalyst, incapability of maintaining the structural integrity of materials, complex control conditions and the like. The curing agent does not need a plurality of response conditions, and can complete recombination only by simple temperature rise (above the glass transition temperature). Meanwhile, based on reversible chemical bonds, the original structure of the material can be maintained, and repeated fracture and reconstruction can be realized, so-called memory effect is realized; flexible synthesis, and is suitable for introducing monomers and resins with various structures.
(2) The epoxy resin cured by the curing agent based on the phenol-urethane bond has good mechanical property and good thermal stability; the epoxy resin can have self-repairing property and reworkability without catalyst or other specific conditions: the self-repairing behavior can be completed within 2 hours at the temperature of 100 ℃; the reworkable condition is simple, the film can be prepared by only pressing and programming the temperature to be within 200 ℃ under a hot pressing instrument, and both characteristics can be realized by multiple times of circulation.
Drawings
FIG. 1 shows a self-healing process of cured epoxy resin, wherein (a) is a self-healing process of PCBs-EP and (b) is a self-healing process of MPBA-EP.
FIG. 2 shows the reworkable process of cured epoxy resin, the reworkable process of PCBs-EP (a), the reworkable process of MPBA-EP (b)
FIG. 3 is a schematic illustration of a 4- (6-hydroxyhexyloxy) phenol monomer 1 H NMR spectrum.
FIG. 4 is an infrared spectrum of a 4- (6-hydroxyhexyloxy) phenol monomer.
FIG. 5 is an infrared spectrum of a curing agent based on a phenol-urethane bond.
FIG. 6 shows an infrared spectrum of PCBs-EP.
FIG. 7 is an infrared spectrum of MPBA (comparative example curative) and TDI.
FIG. 8 is a stress strain curve of PCBs-EP.
FIG. 9 shows DSC curve (a) of PCBs-EP, TGA and DTG curve (b) of PCBs-EP, and DMA dynamic mechanical analysis result (c) of PCBs-EP.
FIG. 10 shows the shape memory cycle of PCBs-EP.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
The raw materials related to the invention can be directly purchased from the market, and the process parameters which are not specially noted can be carried out by referring to the conventional technology.
In examples and comparative examples, cured epoxy resins were tested for repair properties by BX40 polarization microscopy of THMS600E Linkam heating stage equipment: a crack was cut on the surface of the sample with a knife, and then it was heated to 100 ℃ on a heating table, and the repair effect was observed within 2 hours.
In examples and comparative examples, the cured epoxy resin was cut into pieces, and then subjected to hot press molding by a hot press for 150 to 2 hours and 200 to 2 hours, and the reworkability was tested.
The epoxy resin type used in examples and comparative examples was E-51.
Example 1
1. Preparation of phenolic monomers
(1) Under the condition of nitrogen atmosphere reaction, 0.15 mole part of hydroquinone and 0.05 mole part of 6-bromo-n-hexanol are dissolved in 100ml of absolute ethyl alcohol (2.17 mole part) solvent in a reaction bottle, and transferred to an oil bath pot at 60 ℃ for magnetic stirring to form a uniform solution;
(2) Dissolving 0.05 molar part of sodium hydroxide in 18ml (1 molar part) of water solvent, transferring to a constant pressure funnel, placing above a reaction bottle, slowly dripping sodium hydroxide-water solution into the reaction bottle for 2h, and refluxing the whole reaction system for 12h (namely, continuing to react for 10h after the dripping is finished);
(3) After the reaction, cooling at-10 ℃, transferring into a separating funnel, extracting and phase-separating by normal hexane, wherein unreacted 6-bromo-n-hexanol exists in an organic phase, neutralizing an aqueous phase with a small amount of aqueous hydrochloric acid until the pH value is=2, and continuously performing reduced pressure rotary evaporation to remove solvent ethanol, wherein monosubstituted and disubstituted products can be separated out. Washing with water, suction filtering to remove impurities such as p-benzoquinone, dissolving in a small amount of sodium hydroxide solution, and filtering to obtain filtrate. The di-substituted byproducts and other impurities are removed by using dichloromethane extraction, hydrochloric acid is used again to neutralize to pH=2 so as to separate out phenolic products, after multiple times of water washing and suction filtration, the phenolic products are placed in a vacuum oven at 70 ℃ for drying for 24 hours, and the yield is calculated as follows: 64.13%. The structural formula and nuclear magnetism and infrared spectrograms are shown in figures 3 and 4 of the specification.
2. Preparation of curing agents based on phenol-urethane bonds
(1) Uniformly mixing 0.02 molar part of the phenolic monomer (4- (6-hydroxyhexyloxy) phenol) prepared above with 0.62 molar part of anhydrous tetrahydrofuran solvent to obtain a mixed solution;
(2) Slowly dripping the mixed solution into a reaction bottle containing 0.044 mole parts of TDI and 1.4 mole parts of anhydrous tetrahydrofuran solvent under the condition of nitrogen atmosphere, wherein the mass of dibutyltin dilaurate is 0.5% of the total mass of reactants, the dripping time is 1h, the whole reaction is magnetically stirred in an oil bath pot at 64 ℃ and is condensed and returned for reaction, and the reaction is finished after 3.5h (namely, the reaction is continued for 2.5h after the dripping is finished); the temperature is reduced to 40 ℃;
(3) Uniformly mixing 0.048 mole part of DDM with 0.62 mole part of anhydrous tetrahydrofuran solvent to obtain a mixed solution;
(4) Pouring the DDM-anhydrous tetrahydrofuran mixed solution obtained in the step (3) into a reaction bottle obtained in the step (2) rapidly, magnetically stirring, condensing and refluxing, and reacting for 3h;
(5) After the reaction is finished, filtering to obtain a solid, washing and filtering for multiple times by tetrahydrofuran, and then drying to obtain the curing agent based on the phenol-carbamate bond, wherein the yield is as follows: 54.14%. The structural formula is shown as follows, infrared characteristics are shown in figure 5 of the specification:
3. epoxy curing
(1) 0.01 molar part of the prepared curing agent based on a phenol-urethane bond is dissolved and dispersed in 15ml of N, N-dimethylformamide, and is ultrasonically dispersed for 30min;
(2) Adding 0.04 mol part of epoxy resin, immediately performing ultrasonic dispersion for 15min to uniformly disperse the curing agent in the resin matrix to obtain uniform mixed solution;
(3) Pouring the mixed solution into a mould after vacuum degassing bubble operation, volatilizing the solvent, and then heating to cure, wherein the curing procedure is as follows: curing at 120 ℃ for 3 hours, curing at 150 ℃ for 3 hours, and curing at 180 ℃ for 1 hour to obtain the self-repairing epoxy resin based on phenol-urethane bond dynamic covalent, which is marked as PCBs-EP.
Example 2
1. Preparation of phenolic monomers
(1) Under the reaction condition of nitrogen atmosphere, 0.12 mole part of hydroquinone and 0.05 mole part of 5-chloro-n-amyl alcohol are dissolved in 100ml of absolute ethyl alcohol (2.17 mole parts) solvent in a reaction bottle, and the mixture is transferred into an oil bath kettle at the temperature of 70 ℃ to be magnetically stirred to form a uniform solution;
(2) Dissolving 0.05 molar part of potassium hydroxide in 18ml (1 molar part) of water solvent, transferring to a constant pressure funnel, placing above a reaction bottle, slowly dripping potassium hydroxide-water solution into the reaction bottle for 2h, and refluxing the whole reaction system for 14h (namely, continuing to react for 12h after dripping is finished);
(3) After the reaction is finished, cooling at-10 ℃, transferring into a separating funnel, extracting and phase-separating by normal hexane, wherein unreacted 5-chloro-n-amyl alcohol exists in an organic phase, neutralizing an aqueous phase with a small amount of aqueous hydrochloric acid until the pH value is=2, and continuously performing reduced pressure rotary evaporation to remove solvent ethanol, wherein monosubstituted and disubstituted products can be separated out. After removing impurities such as p-benzoquinone by water washing and suction filtration, dissolving the impurities in a small amount of sodium hydroxide solution, filtering to obtain filtrate, removing disubstituted byproducts and other impurities by using dichloromethane extraction, neutralizing with hydrochloric acid until the pH value is=2 to separate out phenolic products, washing for many times, suction filtering, and drying the phenolic products in a vacuum oven at 70 ℃ for 24 hours, wherein the yield is calculated to be: 64.13%. The structural formula is as follows:
2. preparation of curing agents based on phenol-urethane bonds
(1) Uniformly mixing 0.01 mole part of the phenolic monomer (4- (5-hydroxypentyloxy) phenol) prepared above with 0.7 mole part of anhydrous tetrahydrofuran solvent to obtain a mixed solution;
(2) Slowly dripping the mixed solution into a reaction bottle containing 0.04 mol part of IPDI and 1.5 mol part of anhydrous acetone solvent under the condition of nitrogen atmosphere, and reacting with the mass of dibutyltin dilaurate accounting for 0.5% of the total mass of reactants for 1h, wherein the whole reaction is magnetically stirred in an oil bath pot at 50 ℃ and is condensed and returned for reacting for 5h, and ending the reaction (namely, continuing to react for 4h after the dripping is finished); the temperature is reduced to 35 ℃;
(3) Uniformly mixing 0.06 molar part of DDS with 0.7 molar part of anhydrous acetone solvent to obtain a mixed solution;
(4) Rapidly pouring the DDS-anhydrous acetone mixed solution obtained in the step (3) into the reaction bottle obtained in the step (2), magnetically stirring, condensing and refluxing, and reacting for 5 hours;
(5) After the reaction is finished, filtering to obtain a solid, washing with tetrahydrofuran for multiple times, filtering and drying to obtain the curing agent based on the phenol-carbamate bond, wherein the yield is as follows: 54.14%. The structural formula is as follows:
3. epoxy curing
(1) 0.01 molar part of the prepared curing agent based on a phenol-urethane bond is dissolved and dispersed in 15ml of N, N-dimethylformamide, and is ultrasonically dispersed for 30min;
(2) Adding 0.06 mol part of epoxy resin, immediately performing ultrasonic dispersion for 15min to uniformly disperse the curing agent in the resin matrix to obtain uniform mixed solution;
(3) Pouring the mixed solution into a mould after vacuum degassing bubble operation, volatilizing the solvent, and then heating to cure, wherein the curing procedure is as follows: curing for 4h at 90 ℃, curing for 3h at 140 ℃ and curing for 2h at 170 ℃ to obtain the self-repairing epoxy resin based on phenol-urethane bond dynamic covalent, which is marked as PCBs-EP-1.
Example 3
1. Preparation of phenolic monomers
Commercial 4,4' -dihydroxydiphenyl ether was selected as the phenolic monomer.
2. Preparation of curing agents based on phenol-urethane bonds
(1) Uniformly mixing 0.01 molar part of 4,4' -dihydroxydiphenyl ether with 1 molar part of anhydrous tetrahydrofuran solvent to obtain a mixed solution;
(2) Slowly dripping the mixed solution into a reaction bottle containing 0.03 mol part of IPDI and 1.5 mol parts of anhydrous tetrahydrofuran solvent under the condition of nitrogen atmosphere, and reacting with the mass of dibutyltin dilaurate accounting for 0.5% of the total mass of reactants for 1h, wherein the whole reaction is magnetically stirred in an oil bath pot at 65 ℃ and is condensed and returned for reaction, and finishing the reaction after 6h (namely, continuing to react for 5h after the dripping is finished); the temperature is reduced to 40 ℃;
(3) Uniformly mixing 0.04 part of ODA with 0.7 part of anhydrous tetrahydrofuran solvent to obtain a mixed solution;
(4) Pouring the ODA-anhydrous tetrahydrofuran mixed solution obtained in the step (3) into a reaction bottle obtained in the step (2) rapidly, magnetically stirring, condensing and refluxing, and reacting for 6 hours;
(5) After the reaction is finished, filtering to obtain a solid, washing and filtering for multiple times by tetrahydrofuran, and then drying to obtain the curing agent based on the phenol-carbamate bond, wherein the yield is as follows: 54.14%. The structural formula is as follows:
2. epoxy curing
(1) 0.01 molar part of the prepared curing agent based on a phenol-urethane bond is dissolved and dispersed in 15ml of N, N-dimethylformamide, and is ultrasonically dispersed for 30min;
(2) Adding 0.04 mol part of epoxy resin, immediately performing ultrasonic dispersion for 15min to uniformly disperse the curing agent in the resin matrix to obtain uniform mixed solution;
(3) Pouring the mixed solution into a mould after vacuum degassing bubble operation, volatilizing the solvent, and then heating to cure, wherein the curing procedure is as follows: curing at 130 ℃ for 2 hours, at 160 ℃ for 2 hours, and at 200 ℃ for 1 hour to obtain the self-repairing epoxy resin based on phenol-urethane bond dynamic covalent, which is marked as PCBs-EP-2.
Comparative example 1
1. Preparation of curing agent
(1) Under the condition of nitrogen atmosphere, 10 mole parts of DDM is dissolved in 6 mole parts of anhydrous THF solvent in a reaction bottle, and the solution is transferred into a constant temperature oil bath kettle at 55 ℃ for magnetic stirring to form uniform solution;
(2) 5 mol parts of TDI and 4 mol parts of anhydrous THF are stirred to form a homogeneous solution, the homogeneous solution is transferred into a constant pressure funnel and put above a reaction bottle, the polyurethane prepolymer-anhydrous THF solution is slowly dripped into the reaction bottle, the dripping time is 2h, and the whole reaction system is refluxed for 8h (namely, the reaction is continued for 6h after the dripping is finished);
(3) After the reaction, the mixture was filtered and washed, and dried in an oven at 70℃for 24 hours under vacuum to give a white solid powder designated as 1,1' - (4-methyl-1, 3-phenylene) bis (3- (4- (4-aminobenzyl) phenyl) urea) as MPBA. The MPBA structural formula is shown below:
2. epoxy curing
(1) Dissolving and dispersing 7 mole parts of MPBA prepared in the step one and 3 mole parts of DDM cross-linking agent in 5ml of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min;
(2) Adding 10 mol parts of epoxy resin, immediately performing ultrasonic dispersion for 15min to uniformly disperse the cross-linking agent and the curing agent in the resin matrix to obtain uniform mixed solution;
(3) Pouring the mixed solution into a film after vacuum degassing and bubble operation, volatilizing the solvent at room temperature for 12 hours, and then heating to cure, wherein the curing procedure is as follows: curing for 3h at 120 ℃, curing for 3h at 155 ℃ and curing for 1h at 180 ℃ to obtain the thermosetting epoxy resin which is brown and is marked as MPBA-EP.
Each test was conducted on PCBs-EP and MPBA-EP obtained in example 1 and comparative example 1 described above:
as can be seen from fig. 1: after being heated at 100 ℃, PCBs-EP has obvious restoration trend within 20min, and is almost completely restored after 2 h; MPBA-EP scratches, when heated and observed by a microscope, are not repaired, and have no self-repairing performance.
As can be seen from fig. 2: after the PCBs-EP film is cut into fragments, the fragments can be formed again through hot pressing, so that the material has processability; whereas MPBA/EP does not possess processability, indicating that reversible cleavage and recombination of the phenolic-urethane bonds introduced in PCBs-EP materials gives the material dynamic covalent properties.
The nuclear magnetic and infrared results of FIGS. 3 and 4 demonstrate successful synthesis of 4- (6-hydroxyhexyloxy) phenol monomer.
In the IR spectrum of 4- (6-hydroxyhexyloxy) phenol monomer in FIG. 5, 3344cm -1 Is the characteristic absorption peak of the stretching vibration of the phenolic hydroxyl; in TDI, 2270cm -1 Is the telescopic vibration absorption peak of-NCO; in the case of the synthetic cured epoxy resins, however, neither peak section has a distinct characteristic absorption peak, which indicates that the phenolic hydroxyl groups are almost completely reacted with-NCO, and, in addition, at 3284cm -1 N-H characteristic absorption peak at 1710cm -1 The peak of the telescopic vibration absorption at c=o illustrates the synthesis of the phenol-urethane bond.
The degree of cure of the dynamic covalent epoxy resin PCBs-EP is shown in FIG. 6, and the infrared spectrum of PCBs-EP shows that the peak of the urethane carbonyl peak appears at 1710cm -1 Nearby. Furthermore, the epoxy resin was used at 912cm -1 The characteristic peak at which has disappeared. The above infrared spectroscopic results demonstrate that dynamic covalent phenol-urethane linkages have been successfully incorporated into PCBs-EP crosslinked networks.
The disappearance of the characteristic peaks for isocyanate groups and appearance of the characteristic peaks for urea carbonyl groups in FIG. 7 indicate that MPBA was successfully prepared, and FIGS. 5 and 6 have demonstrated that the curing agent based on a phenol-urethane bond can completely cure epoxy resin E-51, and the curing method is equally applicable to MPBA curing epoxy resin E-51 to obtain MPBA/EP, so that infrared characterization is not performed any more.
From FIG. 8, it is known that the tensile strength of PCBs-EP is 95.89MPa, which reaches the tensile strength of common thermosetting epoxy and is more excellent than the mechanical properties of other thermosetting materials constructed by dynamic covalent bonds. The elongation at break of PCBs-EP is 6.90%, which can be explained as follows: during the stretching deformation process, dynamic covalent phenol-carbamate bonds undergo dynamic exchange, so that the movement of molecular chains is limited, and the energy absorption before fracture is reduced, so that the tensile strength of PCBs-EP is increased, and the elongation at break is reduced.
Glass transition temperature (T) g ) An important physical property of thermoset materials in general, which determines the highest temperature for which the material is usedA range of degrees. Thus, DMA and DSC were used to test T for both materials g Values. As shown in (a) and (c) of FIG. 9, there is only one endothermic peak in DSC curve of PCBs-EP, indicating that the epoxy resin has good compatibility with curing agent. In addition, no exotherm was found on the DSC curve, indicating complete curing of the epoxy network, T in the DSC curve g 78.71 ℃. In DMA test, T g 96.96 ℃. T obtained by DMA method g The values are delayed relative to the values obtained by the DSC method (i.e. higher temperatures), and in general the transition temperatures between DSC and DMA experiments may differ by 10-20 ℃. Combining DSC and DMA test results, the material has a lower glass transition temperature, which facilitates its self-healing under mild conditions. Furthermore, the sample has a high storage modulus, but at near the glass transition temperature, the storage modulus of the sample drops drastically, probably due to the cleavage of the phenol-urethane bond in the molecular structure, and the storage modulus tends to 0 due to the destruction of the network structure.
The TGA results are shown in fig. 9 (b), where the initial decomposition temperature is above 200 c, and it is known that the material can exist stably during processing. In addition, degradation temperatures of PCBs-EP with 5% mass loss and 30% mass loss are 240 ℃ and 359 ℃ respectively, which shows that the PCBs-EP has better thermal stability. At 800℃the char formation rate of PCBs-EP was 10.40%. This is associated with the cleavage of the crosslinked network of PCBs-EP, since the dynamic covalent phenol-urethane bonds can be reversibly broken down at high temperatures. The above results indicate that the self-healing epoxy resins synthesized based on phenol-urethane bonds have good thermal properties and competitiveness compared with the common crosslinked covalent polymers. In the DTG curve, a broad endothermic peak was observed at 280-350 ℃, which may be due to decomposition and volatilization of the lower molecular weight epoxy cure. The endothermic peak occurs at 350-450℃in the sample due to cleavage of the urethane bond between the structural units of the sample and evaporation of the phenolic monomer.
Due to glass transition (T g ) The epoxy resin has dual shape memory when the temperature is lower than T g When PCBs-EP are deformed by external force, the temperature is cooled to T g When the following is aboutThe shape is fixed. When the temporary shape is heated again to be higher than T g When the internal stress is relaxed, the temporary shape returns to the original shape. As shown in FIG. 10, the bars were first heated on a 100℃ hot table for 1min to soften and then bent into a certain "U" shape, which was fixed when the temperature was reduced to room temperature. When the temperature is raised again to 100 ℃, the "U" shape returns to its original flat state within 1min, and then returns according to the same "heat-cool" procedure, and the process can be repeated for at least five cycles without significant change in amplitude. The dynamic phenol-urethane bonds in PCBs-EP can be reversibly cleaved and recombined in response to temperature. In addition, the mobility of the molecular chains increases during heating, both of which together drive the shape recovery process of the material.
The above examples are preferred embodiments of the present invention, but 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 made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a curing agent based on a phenol-urethane bond is characterized by comprising the following steps:
under the atmosphere of nitrogen or inert gas, adding difunctional aromatic phenol and halohydrin into a solvent, stirring and dissolving, dropwise adding alkali liquor at 50-70 ℃ for reaction, and dropwise adding 8-14h to obtain phenolic monomers; wherein the mol ratio of the halohydrin, the difunctional aromatic phenol, the alkali liquor and the solvent is 1: (1-4): (0.5-2): (0.5-10);
dropwise adding a mixture of a phenolic monomer and an anhydrous solvent into difunctional isocyanate in a nitrogen or inert gas atmosphere, adding an organotin catalyst accounting for 0.5-1% of the total mass of reactants, magnetically stirring, and reacting at 55-70 ℃ for 2-6h to obtain a phenolic-carbamate bond;
cooling to 30-45 ℃, adding difunctional aromatic amine, and reacting at 30-45 ℃ for 3-6h to obtain a curing agent based on a phenol-carbamate bond; wherein the molar ratio of the phenolic monomer, the anhydrous solvent, the difunctional isocyanate and the difunctional aromatic amine is 1 (0.5-10): 1-4): 1-6.
2. The method for producing a phenol-urethane bond-based curing agent according to claim 1, characterized in that: the difunctional aromatic phenol in the step (1) is a difunctional aromatic phenol with a symmetrical structure, and is hydroquinone, 4 '-dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfone, 4 '-dihydroxydiphenyl ketone and 4,4' -dihydroxydiphenyl propane.
3. The method for producing a phenol-urethane bond-based curing agent according to claim 2, characterized in that: the difunctional aromatic phenol is hydroquinone.
4. The method for producing a phenol-urethane bond-based curing agent according to claim 1, characterized in that: the alkali liquor in the step (1) is monobasic alkali liquor, including sodium hydroxide aqueous solution or potassium hydroxide aqueous solution; the halohydrin is hydrocarbon with the structure of which the number of straight-chain carbon atoms is 4-8, and the tail end of the halohydrin is provided with a chlorine atom or a bromine atom; the solvent is at least one of tetrahydrofuran, absolute ethyl alcohol, water, toluene and acetone.
5. The method for producing a phenol-urethane bond-based curing agent according to claim 1, characterized in that: the difunctional aromatic amine in the step (2) is one of 4,4 '-diaminodiphenyl methane, 4' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone or 4,4' -diaminodiphenyl ketone; the difunctional isocyanate is one of toluene diisocyanate, isophorone diisocyanate or diphenylmethane diisocyanate.
6. The method for producing a phenol-urethane bond-based curing agent according to claim 1, characterized in that: the difunctional aromatic amine in step (2) is 4,4' -diaminodiphenylmethane; the difunctional isocyanate is toluene diisocyanate.
7. The method for producing a phenol-urethane bond-based curing agent according to claim 1, wherein the anhydrous solvent in the step (2) is at least one of tetrahydrofuran, acetone, toluene, N-dimethylformamide and N, N-dimethylacetamide.
8. The phenol-urethane bond-based curing agent prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the curing agent according to claim 8 based on phenol-urethane bonds in epoxy resins and other thermosets.
10. The use according to claim 9, characterized in that: the curing agent based on the phenol-urethane bond is applied to the curing of the epoxy resin, and specifically comprises the following steps: dissolving a curing agent containing a phenol-carbamate bond in an organic solvent, adding epoxy resin, and uniformly dispersing to obtain a mixed solution; vacuum defoamation is carried out on the mixed solution, and then the mixed solution is transferred into a die for heating and solidification; the curing procedure is specifically as follows: curing for 2-4h at 90-130 ℃, 1-4h at 140-160 ℃ and 0.5-2h at 170-200 ℃ to obtain the dynamic covalent self-repairing epoxy resin based on the phenol-carbamate bond; wherein, the mole ratio of the curing agent to the epoxy resin is 1: (2-6).
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