CN114605604A - Curing agent with ionic liquid structure and preparation method and application thereof - Google Patents
Curing agent with ionic liquid structure and preparation method and application thereof Download PDFInfo
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- CN114605604A CN114605604A CN202210102856.4A CN202210102856A CN114605604A CN 114605604 A CN114605604 A CN 114605604A CN 202210102856 A CN202210102856 A CN 202210102856A CN 114605604 A CN114605604 A CN 114605604A
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- Prior art keywords
- curing agent
- compound
- ionic liquid
- halogen
- structural unit
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 82
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 aliphatic aldehyde compounds Chemical class 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 34
- 150000002367 halogens Chemical class 0.000 claims abstract description 34
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 5
- 150000001412 amines Chemical group 0.000 claims abstract 4
- 238000000576 coating method Methods 0.000 claims description 22
- 239000004814 polyurethane Substances 0.000 claims description 21
- 229920002635 polyurethane Polymers 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 150000003512 tertiary amines Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 150000003141 primary amines Chemical group 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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 10
- 238000000746 purification Methods 0.000 claims description 10
- 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
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 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
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004078 waterproofing Methods 0.000 claims description 6
- 239000007788 liquid Substances 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
- 238000000605 extraction Methods 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 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
- 125000000217 alkyl 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
- 230000006837 decompression Effects 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
- 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
- 230000009467 reduction Effects 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 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
- 239000003973 paint Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 230000036541 health Effects 0.000 abstract description 2
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 18
- 150000001299 aldehydes Chemical class 0.000 description 17
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 12
- FNIFQOISPAAFQF-UHFFFAOYSA-N 4-(chloromethyl)benzaldehyde Chemical compound ClCC1=CC=C(C=O)C=C1 FNIFQOISPAAFQF-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 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
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 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
- 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
- 238000004132 cross linking 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
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 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
- 239000000463 material Substances 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
- 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
- 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 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
- 239000004202 carbamide Substances 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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 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
- 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Images
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
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- 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, and a preparation method and application thereof. The curing agent comprises three structural units: structural units (A) derived from halogen-containing aliphatic aldehyde compounds and/or halogen-containing aromatic aldehyde compounds; a structural unit (B) derived from a compound containing a tertiary amine structure; a structural unit (C) derived from a compound containing a primary amine structure and/or a compound containing an alcoholic amine structure; the structural unit (B) and the structural unit (C) are each covalently linked to the structural unit (A). The invention solves the problems that the existing latent curing agent has large pungent smell and harms the environment and the health of constructors, and simultaneously has the functions of eliminating bubbles and quick curing effect.
Description
Technical Field
The invention belongs to the field of waterproof paint preparation, and particularly relates to a curing agent with an ionic liquid structure, and a preparation method and application thereof.
Background
The polyurethane waterproof coating is generally accepted in the field of building waterproofing due to excellent mechanical property, dilute acid and alkali corrosion resistance and firm bonding with concrete. Compared with a double-component polyurethane waterproof coating which needs to be mixed in advance according to a certain proportion, the single-component polyurethane waterproof coating does not need to be stirred before construction, can be used after being opened, and has lower requirements on constructors, so that the single-component polyurethane waterproof coating is the one with the largest sales volume in the polyurethane waterproof coating.
The single-component polyurethane waterproof coating on the market at present is basically formed into an elastic compact waterproof film through the reaction with moisture in the air and the crosslinking and curing. The basic curing mechanism is that partial isocyanate (-NCO) groups of the prepolymer in the coating react with moisture to generate carbon dioxide gas and primary amine (-NH)2) The group, primary amine group, reacts rapidly with the remaining isocyanate groups to produce urea linkages for chain extension curing (as shown in figure 1). Carbon dioxide gas is inevitably generated in the process, which is also a reason that the coating is easy to generate defects such as bubbles and pinholes. The defects of the coating can greatly reduce the waterproof effect and influence the construction quality.
To address this problem, it is now common practice to add a certain amount of latent curing agent to the coating formulation. The latent curing agent can stably exist in the coating during storage, can generate amino or hydroxyl containing active hydrogen when being hydrolyzed when meeting moisture during construction, can be reacted with isocyanate in advance before the isocyanate is reacted 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 coating added with the common latent curing agent reduces or even eliminates the generation of bubbles, the problem of strong pungent smell is also brought, particularly the problem is more obvious in the space with unsmooth air circulation, and the construction experience and the customer impression of the single-component polyurethane waterproof coating are seriously influenced (as shown in figure 2).
The ionic liquid is a salt micromolecule which is liquid at normal temperature (or below 100 ℃), and is different from ordinary micromolecules formed on the basis of hydrogen bonds or Van der Waals force, because of the existence of the ionic bonds, the boiling point of the ionic liquid is very high, and the saturated vapor pressure at the normal temperature is basically zero. 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, the main purpose is to rapidly cure epoxy resin at normal temperature, and the curing agent is liquid in a wide temperature range, so that the curing agent is convenient to mix and stir.
Therefore, in order to enable the latent curing agent in the one-component polyurethane coating or sealant to have the bubble elimination function and the rapid curing effect at the same time and greatly reduce the pungent odor of the one-component polyurethane waterproof coating or sealant, a novel curing agent based on an ionic liquid structure is urgently needed to be provided.
Disclosure of Invention
The invention aims to provide a curing agent with an ionic liquid structure, a preparation method and application aiming at the defects of the prior art. The invention solves the problems that the prior latent curing agent has strong pungent smell and harms the environment and the health of constructors, and simultaneously has the functions of eliminating bubbles and quick curing.
In order to achieve the above object, a first aspect of the present invention provides a curing agent containing an ionic liquid structure, the curing agent comprising three structural units:
(1) structural units (A) derived from halogen-containing aliphatic aldehyde compounds and/or halogen-containing aromatic aldehyde compounds;
(2) a structural unit (B) derived from a compound containing a tertiary amine structure;
(3) a structural unit (C) derived from a compound containing a primary amine structure and/or a compound containing an alcoholic amine structure;
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 covalently linked by an addition reaction of nitrogen in the tertiary amine structure-containing compound with halogen in a halogen-containing aliphatic aldehyde compound and/or a halogen-containing aromatic aldehyde compound, and the structural unit (C) and the structural unit (a) are covalently linked by a reaction of a primary amine structure-containing compound and/or an alcohol amine structure-containing compound with aldehyde groups in a halogen-containing aliphatic aldehyde compound and/or a halogen-containing aromatic aldehyde compound to generate an aldimine or oxazolidine structure containing a plasma liquid structure.
In the present invention, the curing agent of the present invention has an active C ═ N imine structure or a five-membered heterocyclic (oxazolidine) structure containing an oxynitride, and when reacted with moisture, is hydrolyzed to produce an amino group or/and a hydroxyl group. Then, amino or/and hydroxyl and isocyanic acid radical (-NCO) chain extension crosslinking of polyurethane prepolymer; the curing agent of the invention generates ionic liquid aldehyde when reacting with moisture, the vapor pressure is low, the volatile is difficult, no VOC is provided, and the problem of pungent odor released in the curing process of polyurethane coating is solved. In the present invention, the process of a curing agent hydrolysis reaction of the present invention is shown in fig. 3.
According to the invention, preferably, the halogen-containing aliphatic aldehydes have the general formula X-R1-CHO, wherein R1Is selected from C2-C6And X is chlorine or bromine.
According to the present invention, it is preferable that the halogen-containing aromatic aldehyde compound has a general formula 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, - (CH) of the general formula (1)2)n-X is- (CH)2)m-meta or para to CHO.
According to the invention, preferably, the compound containing a tertiary amine structure is a fatty 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 fatty tertiary amine has a general formula of N (R)2)3，R2Each independently is C1-C8Alkyl groups of (a); it is preferable to select 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 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 aliphatic primary 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 of 0 to 10, preferably 0 to 3.
According to the invention, preferably, the general formula of the compound containing the alcohol amine structure is shown as the formula (3):
wherein R is C2-C6Linear or branched alkyl of (a); preferably at least one of ethyl, propyl, isopropyl, n-butyl and isobutyl.
The second aspect of the present invention provides a preparation method of the curing agent containing an ionic liquid structure, which comprises the following steps:
the halogen-containing aliphatic aldehyde compound and/or the halogen-containing aromatic aldehyde compound are/is firstly reacted with one of the compound containing the tertiary amine structure and the compound containing the primary amine structure and/or the compound containing the alcoholic amine structure, and the obtained product is further reacted with the other compound to obtain the curing agent containing the ionic liquid structure.
According to the invention, preferably, the method is one of the following:
the first method is as follows:
s1: mixing the halogen-containing aliphatic 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 ℃, reacting in a nitrogen atmosphere, and sequentially carrying out decompression and extraction and purification treatment by using dichloromethane to obtain an aldehyde compound containing an ionic liquid structure; the first organic solvent is preferably anhydrous tetrahydrofuran;
s2: uniformly stirring and mixing the compound containing the primary amine and/or alcohol amine structure and a second organic solvent at 55-65 ℃ to obtain a second mixed system; dropwise adding 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 separation condensation and reduced pressure distillation purification treatment to obtain the curing agent with the ionic liquid structure; the second organic solvent is preferably cyclohexane;
the second method comprises the following steps:
s1: uniformly stirring and mixing the compound containing the primary amine and/or alcohol amine structure and a second organic solvent at 55-65 ℃ to obtain a first mixed system; dropwise adding the halogen-containing aliphatic 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 a first organic solvent to obtain a third mixed system; heating the third mixed system to 55-65 ℃, reacting in a nitrogen atmosphere, and then sequentially carrying out pressure reduction and extraction and purification treatment 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 embodiment, taking pentanediamine, p-chloromethylbenzaldehyde and N-methylimidazole as an example, the preparation method of the second mode is specifically as follows:
s1: 102g of pentamethylene diamine (1mol) were added to 300ml of cyclohexane and stirred at 60 ℃. 309 g of p-chloromethylbenzaldehyde (2mol) was slowly added dropwise over 30 to 60 minutes. Heating to 110 ℃, carrying out water diversion and condensation on water generated by the reaction, completely reacting when the generated water reaches a theoretical value, and carrying out reduced pressure distillation and purification to obtain an aldimine liquid product.
S2: 375 g of aldimine liquid product (1mol) and 193ml of N-methylimidazole (2.42mol) were dissolved in 0.8L of dry tetrahydrofuran and reacted at elevated temperature to 60 ℃ for 24 hours under a nitrogen atmosphere. Then volatile substances (including the solvent and unreacted raw materials) are removed under reduced pressure, and the viscous lower-layer substance is extracted by dichloromethane and purified 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 yellow transparent liquid.
The invention provides an application of the curing agent containing the ionic liquid structure in preparing a one-component polyurethane waterproof coating and/or sealant.
The technical scheme of the invention has the following beneficial effects:
the curing agent inherits the bubble elimination function and the quick curing effect of the common latent curing agent on the market, and meanwhile, the aldehyde ionic liquid generated by hydrolysis does not volatilize into the air due to the existence of ionic bonds and is locked in the coating to serve as an inert filler, so that the pungent smell caused by the release of 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 above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a schematic view of a curing mechanism of a conventional one-component polyurethane waterproof coating material.
Fig. 2 shows a schematic of the hydrolysis process of a prior art latent curing agent.
FIG. 3 shows a process diagram of the hydrolysis reaction of the 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 in example 3 of the present invention.
FIG. 7 shows a structural diagram of a curing agent containing an ionic liquid structure in example 4 of the present invention.
FIG. 8 is a structural diagram showing a curing agent containing an ionic liquid structure in example 5 of the present invention.
FIG. 9 is a structural diagram showing a curing agent containing an ionic liquid structure in example 6 of the present invention.
FIG. 10 shows a schematic view of the synthesis process of a structural unit (A) derived from a halogen-containing aliphatic aldehyde compound and/or a halogen-containing aromatic aldehyde compound and a structural unit (B) derived from a compound containing a tertiary amine structure according to the present invention, and the composition thereof.
FIG. 11 shows a schematic diagram of the synthesis of the composition of FIG. 10 and a structural unit (C) derived from a compound containing a primary amine structure and/or a compound containing an alcohol amine structure of the present invention, and the composition.
FIG. 12 shows a schematic diagram of the synthesis of the composition of FIG. 10 and a structural unit (C) derived from a compound containing a primary amine structure and/or a compound containing an alcohol amine structure of the present invention, and the composition.
FIG. 13 shows a 1H-NMR spectrum (nuclear magnetic resonance) of an aldehyde containing an ionic liquid structure synthesized from chloromethylbenzaldehyde and N-methylimidazole of 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 of example 1 of the present invention.
Fig. 15 shows an FTIR spectrum (infrared spectrum) of the curing agent containing an ionic liquid structure of example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by 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
This example provides a curing agent containing an ionic liquid structure, as shown in fig. 4, the curing agent 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: mixing 480g (3.1mol) of p-chloromethylbenzaldehyde, 300ml (3.76mol) of N-methylimidazole and 1L of anhydrous tetrahydrofuran, heating to 60 ℃, reacting for 24 hours in a nitrogen atmosphere, removing volatile substances (including the anhydrous tetrahydrofuran and unreacted raw materials) under reduced pressure, extracting viscous lower-layer substances by using dichloromethane, and purifying to obtain aldehyde containing an ionic liquid structure;
s2: 102g (1mol) of 2-methylpentanediamine and 300ml of cyclohexane are stirred and mixed evenly at the temperature of 60 ℃ to obtain a 2-methylpentanediamine solution; 473g (2mol) of the aldehyde containing the ionic liquid structure obtained in S1 is added dropwise into the 2-methylpentanediamine solution within 30-60min, the temperature is raised to 110 ℃ for reaction, and water generated in the reaction is collected by water condensation. 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
This example provides a curing agent containing an ionic liquid structure, as shown in fig. 5, the curing agent includes three structural units:
(1) m-chloromethylbenzaldehyde;
(2) tri-n-butylamine;
(3) pentanediamine.
The preparation method of the curing agent containing the ionic liquid structure of the embodiment is different from that of the embodiment 1 only in that: s1: the molar ratio of the m-chloromethylbenzaldehyde to the tri-n-butylamine is 1:1.21, and aldehyde containing an ionic liquid structure is obtained;
s2: the molar ratio of the aldehyde containing the ionic liquid structure to the pentanediamine is 1:1.
Example 3
This example provides a curing agent containing an ionic liquid structure, as shown in fig. 6, the curing agent 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 of the embodiment is different from that of the embodiment 1 only in that: s1: the molar ratio of the 2-methyl-3-chloropropionaldehyde to the N-methylimidazole is 1:1.21, so that aldehyde containing an ionic liquid structure is obtained;
s2: the molar ratio of the aldehyde containing the ionic liquid structure to the 2-methylpentamethylene diamine is 1:1.
Example 4
This example provides a curing agent containing an ionic liquid structure, as shown in fig. 7, the curing agent 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 of the embodiment is different from that of the embodiment 1 only in that: s1: the molar ratio of the p-chloromethylbenzaldehyde to the 4-methylpyridine is 1:1.21, and aldehyde containing an ionic liquid structure is obtained;
s2: the dosage molar ratio of the aldehyde containing the ionic liquid structure to the N-isopropyl ethanolamine is 1:1.
Example 5
This example provides a curing agent containing an ionic liquid structure, as shown in fig. 8, the curing agent includes three structural units:
(1) p-chloromethyl benzaldehyde;
(2) 4-methylpyridine;
(3) n-ethyl ethylene diamine.
The preparation method of the curing agent containing the ionic liquid structure of the embodiment is different from that of the embodiment 1 only in that: s1: the molar ratio of the p-chloromethylbenzaldehyde to the 4-methylpyridine is 1:1.21, and aldehyde containing an ionic liquid structure is obtained;
s2: the molar ratio of the aldehyde containing the ionic liquid structure to the N-ethyl ethylenediamine is 1:1.
Example 6
This example provides a curing agent containing an ionic liquid structure, as shown in fig. 9, the curing agent 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 of the embodiment is different from that of the embodiment 1 only in that: s1: the molar ratio of the p-chloromethylbenzaldehyde to the 4-methylpyridine is 1:1.21, and aldehyde containing an ionic liquid structure is obtained;
s2: the dosage molar ratio of the aldehyde containing the ionic liquid structure to the 1, 4-diaminocyclohexane is 1:1.
Test example
As shown in Table 1, formulations of one-part polyurethane waterproofing coatings were synthesized for the curing agents of examples 1-6. And formulations of the one-component polyurethane waterproofing coatings of comparative examples 1-2. In comparative example 2, ALT-401 latent curing agent from Ailite, Hunan was used.
TABLE 1
| Raw materials (parts by mass) | Comparative example 1 | Comparative example 2 | Examples 1 to 6 |
| |
21 | 21 | 21 |
| |
6 | 6 | 6 |
| |
13 | 13 | 13 |
| Dispersing agent | 0.2 | 0.2 | 0.2 |
| |
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 |
| |
0 | 2 | 2 |
| Defoaming agent | 0.2 | 0.2 | 0.2 |
| Isopar solvent | 7 | 7 | 7 |
| Total of | 98.9 | 100.9 | 100.9 |
This test example the procedure for synthesizing one-part polyurethane waterproof paint using the curing agents of examples 1 to 6 and comparative examples 1 to 2, respectively, includes: firstly, polyether polyol, a plasticizer, a dispersing agent, talcum powder and heavy calcium are stirred and mixed, the temperature is increased to 120 ℃, dehydration is carried out for 3 hours, the water content is reduced to be lower than 0.03%, then the temperature is reduced to 60 ℃, isocyanate (TDI-80) is added, stirring is carried out uniformly, the temperature is increased to 80 ℃, reaction is carried out 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 waterproofing paints synthesized from the curing agents of examples 1 to 6 and the one-component polyurethane waterproofing paints of comparative examples 1 to 2 were cured under standard conditions (23. + -. 2 ℃ C., 50. + -. 10% relative humidity) for 7 days to give mechanical properties, odor of the paints, and film-forming quality as shown in Table 2. The test method adopts GB/T19250 and 2013 polyurethane waterproof paint.
TABLE 2
As can be seen from Table 2, the mechanical properties of the one-component polyurethane waterproof coatings synthesized by the curing agents of comparative examples 1-2 and examples 1-6 meet the performance index requirements of one-component type I of GB/T19250-. Comparative example 1 was good in performance but had many bubbles because no latent curing agent was used. Comparative example 2 benzaldehyde, which has high film-forming quality but emits an unpleasant odor during curing of the coating material. Examples 1 to 6 all achieve the object of reducing odor and improving film formation quality.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not 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 described embodiments.
Claims (10)
1. The curing agent containing an ionic liquid structure is characterized by comprising three structural units:
(1) structural units (A) derived from halogen-containing aliphatic aldehyde compounds and/or halogen-containing aromatic aldehyde compounds;
(2) a structural unit (B) derived from a compound containing a tertiary amine structure;
(3) a structural unit (C) derived from a compound containing a primary amine structure and/or a compound containing an alcoholic amine structure;
the structural unit (B) and the structural unit (C) are each covalently linked to the structural unit (a).
2. The curing agent containing an ionic liquid structure according to claim 1, wherein the structural unit (B) and the structural unit (a) are covalently linked by an addition reaction of nitrogen in the tertiary amine structure-containing compound with halogen in a halogen-containing aliphatic aldehyde compound and/or a halogen-containing aromatic aldehyde compound, and the structural unit (C) and the structural unit (a) are covalently linked by a reaction of a primary amine structure-containing compound and/or an alcohol amine structure-containing compound with aldehyde group in a halogen-containing aliphatic aldehyde compound and/or a halogen-containing aromatic aldehyde compound to form an aldimine or oxazolidine structure containing a plasma liquid structure.
3. The curing agent containing an ionic liquid structure according to claim 1,
the general formula of the halogen-containing aliphatic aldehyde compound is X-R1-CHO, wherein R1Is selected from C2-C6And X is chlorine or bromine.
4. The curing agent containing an ionic liquid structure according to claim 1,
the general formula of the halogen-containing aromatic aldehyde compound is shown as a 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.
5. The curing agent containing an ionic liquid structure according to claim 1, wherein the compound containing a tertiary amine structure is a fatty 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 fatty tertiary amine has a general formula of N (R)2)3，R2Each independently is C1-C8Alkyl groups of (a); it is preferably at least one selected from the group consisting of N, N-diisopropylethylamine, triethylamine, N-dimethylethylamine, tri-N-butylamine, tri-N-octylamine, and triisopropylamine.
6. The curing agent containing an ionic liquid structure according to claim 1,
the compound containing the primary amine structure is a compound containing more than two amine structures; preferably 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 aliphatic primary 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 of 0 to 10, preferably 0 to 3.
7. The curing agent containing an ionic liquid structure according to claim 1,
the general formula of the compound containing an alcohol amine structure is shown as a formula (3):
wherein R is a linear or branched alkyl of C2-C6; preferably at least one of ethyl, propyl, isopropyl, n-butyl and isobutyl.
8. The method for preparing the curing agent containing an ionic liquid structure according to any one of claims 1 to 7, comprising the steps of:
the halogen-containing aliphatic aldehyde compound and/or the halogen-containing aromatic aldehyde compound are/is firstly reacted with one of the compound containing the tertiary amine structure and the compound containing the primary amine structure and/or the compound containing the alcoholic amine structure, and the obtained product is further reacted with the other compound to obtain the curing agent containing the ionic liquid structure.
9. The method for preparing the curing agent containing the ionic liquid structure according to claim 8, wherein the method adopts one of the following modes:
the first method is as follows:
s1: mixing the halogen-containing aliphatic 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 ℃, reacting in a nitrogen atmosphere, and sequentially carrying out decompression and extraction and purification treatment by using dichloromethane to obtain an aldehyde compound containing an ionic liquid structure; the first organic solvent is preferably anhydrous tetrahydrofuran;
s2: uniformly stirring and mixing the compound containing the primary amine and/or alcohol amine structure and a second organic solvent at 55-65 ℃ to obtain a second mixed system; dropwise adding 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 separation condensation and reduced pressure distillation purification treatment to obtain the curing agent with the ionic liquid structure; the second organic solvent is preferably cyclohexane;
the second method comprises the following steps:
s1: uniformly stirring and mixing the compound containing the primary amine and/or alcohol amine structure and a second organic solvent at 55-65 ℃ to obtain a first mixed system; dropwise adding the halogen-containing aliphatic 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 a first organic solvent to obtain a third mixed system; heating the third mixed system to 55-65 ℃, reacting in a nitrogen atmosphere, and then sequentially carrying out pressure reduction and extraction and purification treatment by using dichloromethane to obtain the curing agent with the ionic liquid structure; the first organic solvent is preferably anhydrous tetrahydrofuran.
10. Use of the curing agent containing an ionic liquid structure according to any one of claims 1 to 7 for the preparation of one-component polyurethane waterproofing coatings 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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