CN114605604B - Curing agent with ionic liquid structure, preparation method and application - Google Patents
Curing agent with ionic liquid structure, preparation method and application Download PDFInfo
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- CN114605604B CN114605604B CN202210102856.4A CN202210102856A CN114605604B CN 114605604 B CN114605604 B CN 114605604B CN 202210102856 A CN202210102856 A CN 202210102856A CN 114605604 B CN114605604 B CN 114605604B
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- curing agent
- ionic liquid
- liquid structure
- compound
- halogen
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 85
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 34
- 150000002367 halogens Chemical class 0.000 claims abstract description 34
- 239000003973 paint Substances 0.000 claims abstract description 15
- 150000002192 fatty aldehydes Chemical class 0.000 claims abstract description 7
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 3
- -1 fatty aldehyde compound Chemical class 0.000 claims description 39
- 239000004814 polyurethane Substances 0.000 claims description 22
- 229920002635 polyurethane Polymers 0.000 claims description 22
- 150000003141 primary amines Chemical group 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 150000003512 tertiary amines Chemical group 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 150000004705 aldimines Chemical class 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Chemical group 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000160 oxazolidinyl group Chemical group 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000003139 primary aliphatic amines Chemical class 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 150000003235 pyrrolidines Chemical class 0.000 claims description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004078 waterproofing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 150000001412 amines Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000036541 health Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 17
- 238000000576 coating method Methods 0.000 description 15
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 7
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 6
- FNIFQOISPAAFQF-UHFFFAOYSA-N 4-(chloromethyl)benzaldehyde Chemical compound ClCC1=CC=C(C=O)C=C1 FNIFQOISPAAFQF-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical group 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RILLZYSZSDGYGV-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanol Chemical compound CC(C)NCCO RILLZYSZSDGYGV-UHFFFAOYSA-N 0.000 description 2
- GPNAKRWHQNYWMY-UHFFFAOYSA-N 3-(chloromethyl)benzaldehyde Chemical compound ClCC1=CC=CC(C=O)=C1 GPNAKRWHQNYWMY-UHFFFAOYSA-N 0.000 description 2
- MIGQGYPWOONPRH-UHFFFAOYSA-N 3-chloro-2-methylpropanal Chemical compound ClCC(C)C=O MIGQGYPWOONPRH-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- QQJODMUSGDSKPF-UHFFFAOYSA-N 2-(chloromethyl)benzaldehyde Chemical compound ClCC1=CC=CC=C1C=O QQJODMUSGDSKPF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 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 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004849 latent hardener Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004588 polyurethane sealant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of waterproof paint preparation, and discloses a curing agent with an ionic liquid structure, a preparation method and application thereof. The curing agent comprises three structural units: structural units (a) derived from halogen-containing fatty aldehydes and/or halogen-containing aromatic aldehydes; structural units (B) derived from compounds containing tertiary amine structures; structural units (C) derived from compounds containing primary amine structures and/or compounds containing alcohol amine structures; the structural units (B) and (C) are each covalently linked to the structural unit (A). The invention solves the problems of large pungent smell, environmental hazard and health of constructors of the existing latent curing agent, and has the functions of eliminating bubbles and quick curing.
Description
Technical Field
The invention belongs to the field of waterproof paint preparation, and in particular relates to a curing agent with an ionic liquid structure, a preparation method and application thereof.
Background
Polyurethane waterproof paint is widely accepted in the field of building waterproofing because of excellent mechanical property, dilute acid and alkali corrosion resistance and firm adhesion with concrete. Compared with a double-component polyurethane waterproof paint which needs to be pre-mixed according to a certain proportion, the single-component polyurethane waterproof paint is free from stirring before construction and can be used after being opened, and the requirement on constructors is lower, so that the double-component polyurethane waterproof paint is the one with the largest sales volume in the polyurethane waterproof paint.
The single-component polyurethane waterproof paint in the current market is basically formed into an elastic compact waterproof film through crosslinking and solidification by reacting with moisture in air. The basic curing mechanism is that carbon dioxide gas and primary amine (-NH) are generated by the reaction of partial terminal isocyanate (-NCO) groups of the prepolymer in the coating with moisture 2 ) The primary amine groups react rapidly with the remaining isocyanate groups to form urea-bond chain-extended curing (as shown in FIG. 1Shown). Carbon dioxide gas is inevitably generated in the process, which is also the reason why the coating is prone to defects such as bubbles and pinholes. The defect of the coating can greatly reduce the waterproof effect and influence the construction quality.
To solve this problem, it is currently common practice to add a certain amount of latent curing agent to the coating formulation. The latent curing agent can exist in the coating stably when stored, generates amino or hydroxyl containing active hydrogen when meeting moisture in construction, can react with isocyanate before the isocyanate reacts with water, and avoids the generation of carbon dioxide gas, thereby fundamentally solving the problem that single-component polyurethane is easy to generate bubbles. However, all latent curing agents currently on the market release volatile ketones or aldehydes during hydrolysis. Therefore, although the single-component polyurethane waterproof paint added with the common latent curing agent reduces or even eliminates the generation of bubbles, the problem of large pungent smell is brought, and particularly the problem is more obvious in a space with unsmooth air circulation, so that the construction experience and the customer look and feel of the single-component polyurethane waterproof paint are seriously influenced (shown in figure 2).
The ionic liquid is a salt type small molecule in liquid state at normal temperature (or below 100 ℃), and unlike the common small molecule formed based on hydrogen bond or Van der Waals force, the ionic liquid has very high boiling point due to the existence of ionic bond, and the saturated vapor pressure is basically zero at normal temperature. WO2018/000125A1 discloses an ionic liquid curing agent for epoxy resins. The main synthesis mode is that polyethylene polyamine reacts with organic acid to form modified amide curing agent, which is mainly used for rapidly curing epoxy resin at normal temperature, and the curing agent is liquid in a wide temperature range, so that the mixing and stirring are convenient.
Therefore, in order to enable the latent curing agent in the single-component polyurethane coating or sealant to have the bubble eliminating function and the rapid curing effect at the same time and greatly reduce the pungent smell of the single-component polyurethane waterproof coating or sealant, a novel curing agent based on an ionic liquid structure is needed to be proposed.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and provides a curing agent with an ionic liquid structure, a preparation method and application thereof. The invention solves the problems of large pungent smell, environmental hazard and health of constructors of the existing latent curing agent, and has the functions of eliminating bubbles and quick curing.
In order to achieve the above object, the present invention provides, in a first aspect, a curing agent containing an ionic liquid structure, the curing agent comprising three structural units:
(1) Structural units (a) derived from halogen-containing fatty aldehydes and/or halogen-containing aromatic aldehydes;
(2) Structural units (B) derived from compounds containing tertiary amine structures;
(3) Structural units (C) derived from compounds containing primary amine structures and/or compounds containing alcohol amine structures;
the structural unit (B) and the structural unit (C) are each covalently linked to the structural unit (A).
According to the present invention, preferably, the structural unit (B) and the structural unit (a) are subjected to an addition reaction with nitrogen in the tertiary amine structure-containing compound and halogen in the halogen-containing fatty aldehyde compound and/or the halogen-containing aromatic aldehyde compound to effect covalent attachment, and the structural unit (C) and the structural unit (a) are subjected to an aldehyde group reaction with the primary amine structure-containing compound and/or the alcohol amine structure-containing compound and the halogen-containing fatty aldehyde compound and/or the halogen-containing aromatic aldehyde compound to generate an aldimine or oxazolidine structure containing an ionic liquid structure to effect covalent attachment.
In the present invention, the curing agent of the present invention contains an active c=n imine structure or contains a nitrogen-oxygen five membered heterocyclic ring (oxazolidine) structure, which hydrolyzes to produce an amino group or/and a hydroxyl group upon reaction with moisture. Subsequently, the amino groups or/and the hydroxyl groups are chain-extended and crosslinked with isocyanate (-NCO) groups of the polyurethane prepolymer; the curing agent disclosed by the invention can be used for simultaneously generating ionic liquid aldehyde when reacting with moisture, has low vapor pressure and is extremely difficult to volatilize, does not provide VOC, and the problem of pungent odor released in the curing process of polyurethane coating is solved. In the present invention, a process of the hydrolysis reaction of the curing agent of the present invention is shown in FIG. 3.
According to the present invention, preferably, the halogen-containing fatty aldehyde compound has the general formula X-R 1 -CHO, wherein R 1 Selected from C 2 -C 6 And X is chlorine or bromine.
According to the present invention, preferably, the general formula of the halogen-containing aromatic aldehyde compound is represented by formula (1):
wherein m is an integer of 0 to 5, n is an integer of 0 to 5, and X is chlorine or bromine.
In the present invention, the- (CH) of the general formula (1) 2 ) n X is- (CH) 2 ) m Meta-or para-position of CHO.
According to the present invention, preferably, the tertiary amine structure-containing compound is an aliphatic tertiary amine and/or a cyclic tertiary amine;
the cyclic tertiary amine is five-membered or six-membered cyclic tertiary amine or a derivative thereof, preferably at least one selected from imidazole, pyridine, pyrazole, oxazole and derivatives thereof, N-substituted derivatives of pyrrole and N-substituted derivatives of pyrrolidine;
the general formula of the fatty tertiary amine is N (R) 2 ) 3 ，R 2 Each independently is C 1 -C 8 Alkyl of (a); preferably at least one selected from the group consisting of N, N-diisopropylethylamine, triethylamine, N-dimethylethylamine, tri-N-butylamine, tri-N-octylamine and triisopropylamine.
According to the present invention, preferably, the primary amine structure-containing compound is a compound containing two or more amine structures; preferably comprises at least one of polyoxyalkylene-polyamine containing two or three amino groups, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, m-xylylenediamine, p-xylylenediamine, isophoronediamine and a primary aliphatic amine represented by the general formula (2);
wherein k and z are each independently an integer from 1 to 10, preferably an integer from 1 to 5; y and L are each independently an integer from 0 to 10, preferably an integer from 0 to 3.
According to the present invention, preferably, the general formula of the alcohol amine structure-containing compound is represented by formula (3):
wherein R is C 2 -C 6 Straight or branched alkyl of (a); preferably at least one of ethyl, propyl, isopropyl, n-butyl and isobutyl.
The second aspect of the invention provides a preparation method of the curing agent containing the ionic liquid structure, which comprises the following steps:
and (3) reacting the halogen-containing fatty aldehyde compound and/or the halogen-containing aromatic aldehyde compound with one of the compound containing a tertiary amine structure and the compound containing a primary amine structure and/or the compound containing an alcohol amine structure, and reacting the obtained product with the other one to obtain the curing agent containing the ionic liquid structure.
According to the invention, the method preferably employs one of the following means:
mode one:
s1: mixing the halogen-containing fatty aldehyde and/or halogen-containing aromatic aldehyde compound, the tertiary amine structure-containing compound and a first organic solvent to obtain a first mixed system; heating the first mixed system to 55-65 ℃ and reacting in a nitrogen atmosphere, and then sequentially decompressing and extracting and purifying by using dichloromethane to obtain an aldehyde compound containing an ionic liquid structure; the first organic solvent is preferably anhydrous tetrahydrofuran;
s2: stirring and uniformly mixing the compound containing primary amine and/or alcohol amine structure and a second organic solvent at 55-65 ℃ to obtain a second mixed system; dripping the aldehyde compound containing the ionic liquid structure into a second mixed system to obtain a third mixed system; heating the third mixed system to 105-115 ℃ for reaction, and sequentially carrying out water diversion condensation and reduced pressure distillation purification treatment to obtain the curing agent with the ionic liquid structure; the second organic solvent is preferably cyclohexane;
mode two:
s1: stirring and uniformly mixing the compound containing primary amine and/or alcohol amine structure and the second organic solvent at 55-65 ℃ to obtain a first mixed system; dropwise adding the halogen-containing fatty aldehyde and/or halogen-containing aromatic aldehyde compound into the first mixed system to obtain a second mixed system; heating the second mixed system to 105-115 ℃ for reaction, and sequentially carrying out water diversion condensation and reduced pressure distillation purification treatment to obtain a liquid product containing an aldimine structure; the second organic solvent is preferably cyclohexane;
s2: mixing the liquid product containing the aldimine structure, the compound containing the tertiary amine structure and the first organic solvent to obtain a third mixed system; heating the third mixed system to 55-65 ℃ and reacting in a nitrogen atmosphere, and then sequentially decompressing and extracting and purifying by using dichloromethane to obtain the curing agent with the ionic liquid structure; the first organic solvent is preferably anhydrous tetrahydrofuran.
In the present invention, as a preferable scheme, using pentylene diamine, p-chloromethylbenzaldehyde and N-methylimidazole as examples, the preparation method of the second mode specifically comprises:
s1: 102g of pentamethylenediamine (1 mol) are added to 300ml of cyclohexane and stirred at 60 ℃. 309 g of p-chloromethylbenzaldehyde (2 mol) were slowly added dropwise, and the addition was completed within 30-60 minutes. Heating to 110 ℃, carrying out water diversion condensation on water generated by the reaction, and carrying out reduced pressure distillation and purification when the generated water reaches a theoretical value to obtain an aldimine liquid product.
S2: 375 g of aldimine liquid product (1 mol) and 193ml of N-methylimidazole (2.42 mol) are dissolved in 0.8L of dry tetrahydrofuran and reacted for 24 hours at 60℃under nitrogen atmosphere. Then volatile substances (including solvent and unreacted raw materials) are removed under the condition of reduced pressure, and the viscous lower layer substance is extracted by methylene dichloride and purified, so as to obtain the curing agent with the ionic liquid structure. The curing agent with the ionic liquid structure obtained in the second mode is viscous yellowish transparent liquid.
The invention provides an application of the curing agent containing the ionic liquid structure in preparing single-component polyurethane waterproof paint and/or sealant.
The technical scheme of the invention has the following beneficial effects:
the curing agent disclosed by the invention inherits the bubble eliminating function and the rapid curing effect of the common latent curing agent in the market, meanwhile, aldehyde ionic liquid generated by hydrolysis does not volatilize into air due to the existence of ionic bonds and is locked in the coating to serve as an inert filler, so that the pungent odor caused by releasing aldehyde or ketone organic matters in the curing process of the single-component polyurethane waterproof coating is greatly reduced, and the effect of reducing VOC can be achieved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
Fig. 1 shows a schematic view of a curing mechanism of a conventional one-component polyurethane waterproof coating.
Fig. 2 shows a schematic diagram of the hydrolysis process of the existing latent curing agent.
FIG. 3 shows a schematic diagram of the hydrolysis reaction of a curing agent containing an ionic liquid structure according to the present invention.
Fig. 4 shows a structural diagram of a curing agent containing an ionic liquid structure according to example 1 of the present invention.
Fig. 5 shows a structural diagram of a curing agent containing an ionic liquid structure according to example 2 of the present invention.
Fig. 6 shows a structural diagram of a curing agent containing an ionic liquid structure according to example 3 of the present invention.
Fig. 7 shows a structural diagram of a curing agent containing an ionic liquid structure according to example 4 of the present invention.
Fig. 8 shows a structural diagram of a curing agent containing an ionic liquid structure according to example 5 of the present invention.
Fig. 9 shows a structural diagram of a curing agent containing an ionic liquid structure according to example 6 of the present invention.
FIG. 10 shows a schematic diagram of the synthesis process and composition of a structural unit (A) derived from a halogen-containing fatty aldehyde compound and/or a halogen-containing aromatic aldehyde compound and a structural unit (B) derived from a tertiary amine structure-containing compound according to the present invention.
FIG. 11 shows a schematic diagram of the synthesis process and the composition of FIG. 10 with structural units (C) derived from a primary amine structure-containing compound and/or an alcohol amine structure-containing compound of the present invention.
FIG. 12 shows a schematic diagram of the synthesis process and composition of FIG. 10 with structural units (C) derived from a primary amine structure-containing compound and/or an alcohol amine structure-containing compound of the present invention.
FIG. 13 shows the 1H-NMR spectrum (nuclear magnetic resonance) of an aldehyde containing an ionic liquid structure synthesized from chloromethylbenzaldehyde and N-methylimidazole in example 1 of the present invention.
FIG. 14 shows a 1H-NMR spectrum (nuclear magnetic resonance) of a curing agent containing an ionic liquid structure according to example 1 of the present invention.
Fig. 15 shows FTIR spectra (infrared spectra) of a curing agent containing an ionic liquid structure according to example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The present embodiment provides a curing agent containing an ionic liquid structure, as shown in fig. 4, which includes three structural units:
(1) P-chloromethyl benzaldehyde;
(2) N-methylimidazole;
(3) 2-methylpentanediamine;
the preparation method of the curing agent containing the ionic liquid structure comprises the following steps:
s1: 480g (3.1 mol) of p-chloromethylbenzaldehyde, 300ml (3.76 mol) of N-methylimidazole and 1L of anhydrous tetrahydrofuran are mixed, the temperature is raised to 60 ℃ and the mixture is reacted for 24 hours under the nitrogen atmosphere, volatile substances (including anhydrous tetrahydrofuran and unreacted raw materials) are removed under reduced pressure, and the viscous lower layer substances are extracted by using methylene dichloride and purified to obtain aldehyde containing an ionic liquid structure;
s2: 102g (1 mol) of 2-methylpentanediamine and 300ml of cyclohexane are stirred and mixed uniformly at 60 ℃ to obtain 2-methylpentanediamine solution; 473g (2 mol) of aldehyde containing an ionic liquid structure obtained in the step S1 is added into the 2-methyl pentanediamine solution dropwise within 30-60min, the temperature is raised to 110 ℃ for reaction, and water generated by the reaction is condensed and collected through water separation. And when the generated water reaches a theoretical value, the reaction is complete, and the product is subjected to reduced pressure distillation and purification treatment to obtain the curing agent with the ionic liquid structure.
Example 2
The present embodiment provides a curing agent containing an ionic liquid structure, as shown in fig. 5, the curing agent includes three structural units:
(1) M-chloromethyl benzaldehyde;
(2) Tri-n-butylamine;
(3) Pentanediamine.
The preparation method of the curing agent containing the ionic liquid structure in this embodiment is different from that in embodiment 1 only in that: s1: the molar ratio of m-chloromethylbenzaldehyde to tri-n-butylamine is 1:1.21, and the aldehyde containing the ionic liquid structure is obtained;
s2: the molar ratio of aldehyde containing ionic liquid structure to the using amount of the pentanediamine is 1:1.
Example 3
The present embodiment provides a curing agent containing an ionic liquid structure, as shown in fig. 6, which includes three structural units:
(1) 2-methyl-3-chloropropionaldehyde;
(2) N-methylimidazole;
(3) 2-methylpentanediamine.
The preparation method of the curing agent containing the ionic liquid structure in this embodiment is different from that in embodiment 1 only in that: s1: the molar ratio of the 2-methyl-3-chloropropionaldehyde to the N-methylimidazole is 1:1.21, and the aldehyde containing the ionic liquid structure is obtained;
s2: the molar ratio of aldehyde containing ionic liquid structure to 2-methyl pentanediamine is 1:1.
Example 4
The present embodiment provides a curing agent containing an ionic liquid structure, as shown in fig. 7, which includes three structural units:
(1) P-chloromethyl benzaldehyde;
(2) 4-methylpyridine;
(3) N-isopropyl ethanolamine.
The preparation method of the curing agent containing the ionic liquid structure in this embodiment is different from that in embodiment 1 only in that: s1: the molar ratio of the dosage of the p-chloromethylbenzaldehyde to the dosage of the 4-methylpyridine is 1:1.21, and the aldehyde containing the ionic liquid structure is obtained;
s2: the molar ratio of aldehyde containing ionic liquid structure to N-isopropyl ethanolamine is 1:1.
Example 5
The present embodiment provides a curing agent containing an ionic liquid structure, as shown in fig. 8, which includes three structural units:
(1) P-chloromethyl benzaldehyde;
(2) 4-methylpyridine;
(3) N-ethyl ethylenediamine.
The preparation method of the curing agent containing the ionic liquid structure in this embodiment is different from that in embodiment 1 only in that: s1: the molar ratio of the dosage of the p-chloromethylbenzaldehyde to the dosage of the 4-methylpyridine is 1:1.21, and the aldehyde containing the ionic liquid structure is obtained;
s2: the molar ratio of aldehyde containing ionic liquid structure to N-ethyl ethylenediamine is 1:1.
Example 6
The present embodiment provides a curing agent containing an ionic liquid structure, as shown in fig. 9, which includes three structural units:
(1) P-chloromethyl benzaldehyde;
(2) 4-methylpyridine;
(3) 1, 4-diaminocyclohexane.
The preparation method of the curing agent containing the ionic liquid structure in this embodiment is different from that in embodiment 1 only in that: s1: the molar ratio of the dosage of the p-chloromethylbenzaldehyde to the dosage of the 4-methylpyridine is 1:1.21, and the aldehyde containing the ionic liquid structure is obtained;
s2: the molar ratio of aldehyde containing ionic liquid structure to 1, 4-diaminocyclohexane is 1:1.
Test case
As shown in Table 1, the formulations of the one-component polyurethane waterproof coatings were synthesized with the curing agents of examples 1 to 6. And the formulation of the one-component polyurethane waterproof paint of comparative examples 1-2. Among them, comparative example 2 used ALT-401 latent hardener from Ailite company of Hunan.
TABLE 1
| Raw material (mass portion) | Comparative example 1 | Comparative example 2 | Examples 1 to 6 |
| Polyether glycol 2000 | 21 | 21 | 21 |
| Polyether triol 330N | 6 | 6 | 6 |
| Plasticizer(s) | 13 | 13 | 13 |
| Dispersing agent | 0.2 | 0.2 | 0.2 |
| Talc powder | 12 | 12 | 12 |
| Heavy calcium carbonate | 35 | 35 | 35 |
| TDI-80 | 4.4 | 4.4 | 4.4 |
| Dibutyl tin dilaurate | 0.1 | 0.1 | 0.1 |
| Latent curing agent | 0 | 2 | 2 |
| Defoaming agent | 0.2 | 0.2 | 0.2 |
| Isopar solvent | 7 | 7 | 7 |
| Totals to | 98.9 | 100.9 | 100.9 |
This test example the procedure for synthesizing one-component polyurethane waterproof paint using the curing agent of examples 1 to 6 and comparative examples 1 to 2, respectively, includes: firstly, polyether polyol, plasticizer, dispersing agent, talcum powder and heavy calcium are stirred and mixed, the temperature is raised to 120 ℃ and dehydrated for 3 hours, the temperature is reduced to 60 ℃ after the water content is lower than 0.03%, isocyanate (TDI-80) is added, the temperature is uniformly stirred and raised to 80 ℃ for 2 hours, and dibutyltin dilaurate is added for continuous reaction for 1 hour. Cooling to 65 ℃, adding the curing agent, the defoaming agent and the Isopar solvent, cooling to 55 ℃, vacuum degassing, and sealing and packaging for later use.
The one-component polyurethane waterproof coatings synthesized by the curing agents of examples 1 to 6 and the one-component polyurethane waterproof coatings of comparative examples 1 to 2 were cured under standard conditions (23.+ -. 2 ℃ C., 50.+ -. 10% relative humidity) for 7 days to obtain mechanical properties, odor of the coatings and film-forming quality conditions as shown in Table 2. The test method adopts GB/T19250-2013 polyurethane waterproof paint.
TABLE 2
As can be seen from Table 2, the mechanical properties of the single-component polyurethane waterproof coatings synthesized by the curing agents of comparative examples 1-2 and examples 1-6 all meet the performance index requirements of the single-component I type of GB/T19250-2013 polyurethane waterproof coating. Comparative example 1 has good properties but has a large number of bubbles because no latent curing agent is used. Comparative example 2 was a benzaldehyde which released an unpleasant odor during the curing of the coating, although the film-forming quality was high. Examples 1-6 all achieved the object of reducing odor and improving film formation quality.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (19)
1. A curing agent comprising an ionic liquid structure, the curing agent comprising three structural units:
(1) Structural units (a) derived from halogen-containing fatty aldehydes and/or halogen-containing aromatic aldehydes;
(2) Structural units (B) derived from compounds containing tertiary amine structures;
(3) Structural units (C) derived from compounds containing primary amine structures and/or compounds containing alcohol amine structures;
the structural unit (B) and the structural unit (A) are subjected to addition reaction through nitrogen in the compound containing the tertiary amine structure and halogen in the halogen-containing fatty aldehyde compound and/or the halogen-containing aromatic aldehyde compound to realize covalent connection, and the structural unit (C) and the structural unit (A) are subjected to reaction through the compound containing the primary amine structure and/or the compound containing the alcohol amine structure and aldehyde groups in the halogen-containing fatty aldehyde compound and/or the halogen-containing aromatic aldehyde compound to generate aldimine or oxazolidine structure containing an ionic liquid structure to realize covalent connection.
2. The ionic liquid structure-containing curing agent according to claim 1, wherein,
the general formula of the halogen-containing fatty aldehyde compound is X-R 1 -CHO, wherein R 1 Selected from C 2 -C 6 And X is chlorine or bromine.
3. The ionic liquid structure-containing curing agent according to claim 1, wherein,
the general formula of the halogen-containing aromatic aldehyde compound is shown as the formula (1):
wherein m is an integer of 0 to 5, n is an integer of 0 to 5, and X is chlorine or bromine.
4. The ionic liquid structure-containing curing agent according to claim 1, wherein the tertiary amine structure-containing compound is an aliphatic tertiary amine and/or a cyclic tertiary amine;
the cyclic tertiary amine is five-membered or six-membered cyclic tertiary amine or derivative thereof;
the general formula of the fatty tertiary amine is N (R) 2 ) 3 ，R 2 Each independently is C 1 -C 8 Is a hydrocarbon group.
5. The ionic liquid structure-containing curing agent according to claim 4, wherein the cyclic tertiary amine is at least one selected from the group consisting of imidazole, pyridine, pyrazole, oxazole and derivatives thereof, N-substituted derivatives of pyrrole and N-substituted derivatives of pyrrolidine.
6. The ionic liquid structure-containing curing agent according to claim 4, wherein the tertiary aliphatic amine is at least one selected from the group consisting of N, N-diisopropylethylamine, triethylamine, N-dimethylethylamine, tri-N-butylamine, tri-N-octylamine and triisopropylamine.
7. The ionic liquid structure-containing curing agent according to claim 1, wherein,
the compound containing primary amine structure is a compound containing more than two amine structures.
8. The ionic liquid structure-containing curing agent according to claim 7, wherein,
the primary amine structure-containing compound includes at least one of polyoxyalkylene-polyamine containing two or three amino groups, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, m-xylylenediamine, p-xylylenediamine, isophoronediamine, and a primary aliphatic amine represented by the general formula (2);
wherein k and z are each independently integers from 1 to 10; y and L are each independently integers from 0 to 10.
9. The ionic liquid structure-containing curing agent according to claim 8, wherein,
k and z are each independently integers from 1 to 5.
10. The ionic liquid structure-containing curing agent according to claim 8, wherein,
y and L are each independently integers from 0 to 3.
11. The ionic liquid structure-containing curing agent according to claim 1, wherein,
the general formula of the compound containing the alcohol amine structure is shown as a formula (3):
wherein R is a C2-C6 linear or branched alkyl group.
12. The ionic liquid structure-containing curing agent according to claim 11, wherein,
r is at least one of ethyl, propyl, isopropyl, n-butyl and isobutyl.
13. The method for preparing a curing agent containing an ionic liquid structure according to any one of claims 1 to 12, comprising the steps of:
and (3) reacting the halogen-containing fatty aldehyde compound and/or the halogen-containing aromatic aldehyde compound with one of the compound containing a tertiary amine structure and the compound containing a primary amine structure and/or the compound containing an alcohol amine structure, and reacting the obtained product with the other one to obtain the curing agent containing the ionic liquid structure.
14. The method for preparing a curing agent containing an ionic liquid structure according to claim 13, wherein the method adopts one of the following modes:
mode one:
s1: mixing the halogen-containing fatty aldehyde and/or halogen-containing aromatic aldehyde compound, the tertiary amine structure-containing compound and a first organic solvent to obtain a first mixed system; heating the first mixed system to 55-65 ℃ and reacting in a nitrogen atmosphere, and then sequentially decompressing and extracting and purifying by using dichloromethane to obtain an aldehyde compound containing an ionic liquid structure;
s2: stirring and uniformly mixing the compound containing primary amine and/or alcohol amine structure and a second organic solvent at 55-65 ℃ to obtain a second mixed system; dripping the aldehyde compound containing the ionic liquid structure into a second mixed system to obtain a third mixed system; heating the third mixed system to 105-115 ℃ for reaction, and sequentially carrying out water diversion condensation and reduced pressure distillation purification treatment to obtain the curing agent with the ionic liquid structure;
mode two:
s1: stirring and uniformly mixing the compound containing primary amine and/or alcohol amine structure and the second organic solvent at 55-65 ℃ to obtain a first mixed system; dropwise adding the halogen-containing fatty aldehyde and/or halogen-containing aromatic aldehyde compound into the first mixed system to obtain a second mixed system; heating the second mixed system to 105-115 ℃ for reaction, and sequentially carrying out water diversion condensation and reduced pressure distillation purification treatment to obtain a liquid product containing an aldimine structure;
s2: mixing the liquid product containing the aldimine structure, the compound containing the tertiary amine structure and the first organic solvent to obtain a third mixed system; heating the third mixed system to 55-65 ℃ and reacting in a nitrogen atmosphere, and then sequentially decompressing and extracting and purifying by using dichloromethane to obtain the curing agent with the ionic liquid structure.
15. The method for producing a curing agent having an ionic liquid structure according to claim 14, wherein the first organic solvent in the first mode is anhydrous tetrahydrofuran.
16. The method for producing a curing agent having an ionic liquid structure according to claim 14, wherein the second organic solvent in the first mode is cyclohexane.
17. The method for preparing a curing agent with an ionic liquid structure according to claim 14, wherein the second organic solvent in the second mode is cyclohexane.
18. The method for producing a curing agent having an ionic liquid structure according to claim 14, wherein the first organic solvent in the second mode is anhydrous tetrahydrofuran.
19. Use of a curing agent containing an ionic liquid structure according to any one of claims 1-12 for the preparation of one-component polyurethane waterproofing paints and/or sealants.
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| CN109251292A (en) * | 2018-07-13 | 2019-01-22 | 重庆科顺化工新材料有限公司 | Latent Curing Agents in Polyurethane and single-component polyurethane water-proof paint and preparation method |
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