CN114940736A - Cycloaliphatic imine latent curing agent and preparation method and application thereof - Google Patents
Cycloaliphatic imine latent curing agent and preparation method and application thereof Download PDFInfo
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- CN114940736A CN114940736A CN202210755164.XA CN202210755164A CN114940736A CN 114940736 A CN114940736 A CN 114940736A CN 202210755164 A CN202210755164 A CN 202210755164A CN 114940736 A CN114940736 A CN 114940736A
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- curing agent
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- latent curing
- imine
- alicyclic
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- 150000002466 imines Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- -1 alicyclic imine Chemical class 0.000 claims abstract description 48
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000004821 distillation Methods 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003729 cation exchange resin Substances 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 230000003712 anti-aging effect Effects 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011973 solid acid Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- KMBMQZQZBOLJHN-UHFFFAOYSA-N 2-methyloxirane;oxolane Chemical compound CC1CO1.C1CCOC1 KMBMQZQZBOLJHN-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 125000000879 imine group Chemical group 0.000 claims 2
- 239000004849 latent hardener Substances 0.000 claims 2
- UHSVROPHFKRJIN-UHFFFAOYSA-N 2-methylcyclopentane-1,1-diamine Chemical compound CC1CCCC1(N)N UHSVROPHFKRJIN-UHFFFAOYSA-N 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 50
- 238000000034 method Methods 0.000 abstract description 9
- 238000013008 moisture curing Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- 238000005187 foaming Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 9
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000004588 polyurethane sealant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 238000003860 storage 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
- C08G18/3253—Polyamines being in latent form
- C08G18/3256—Reaction products of polyamines with aldehydes or ketones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an alicyclic imine latent curing agent, and a preparation method and application thereof. The preparation method comprises the following steps: under the environment of nitrogen gas and air evacuation, 10-30 parts by weight of alicyclic primary amine and 0.5-5 parts by weight of catalyst A are mixed, stirred and heated to 40-120 ℃, then 5-30 parts by weight of aldehyde/ketone compound are dripped, and the heat preservation reaction is carried out for 6-15 hours; standing the reaction solution for a certain time, removing water generated in the reaction, and filtering and recovering the catalyst A to obtain a crude product; and (3) carrying out a stepped pressure-variable distillation mode combining atmospheric distillation and reduced pressure distillation on the crude product to recover excessive aldehyde/ketone compounds, and simultaneously distilling to remove water and other impurities to obtain the high-purity alicyclic imine latent curing agent. The cycloaliphatic imine latent curing agent prepared by the method can be applied to a single-component moisture-curing polyurethane system, can solve the foaming problem of the polyurethane system in the moisture curing process, and can also be applied to products such as a bi-component polyurethane system and the like.
Description
Technical Field
The invention relates to a curing agent, in particular to an alicyclic imine latent curing agent and a preparation method thereof, belonging to the technical field of polymer chemistry.
Background
In recent years, new polyurethane materials such as polyurethane waterproof coatings, sealing adhesives and the like are developed rapidly, and particularly single-component moisture-curable polyurethane (SPU) materials are developed rapidly, because SPU does not need to be added with a cross-linking agent or a curing agent and other additives additionally when in use, namely, problems of metering errors and mixing uniformity of all components do not exist, SPU can be cured rapidly only by trace moisture in air, construction difficulty is greatly reduced, and the SPU is particularly wide in application range and field.
Limited by the self-curing mechanism, isocyanate-terminated SPU prepolymers generate CO during moisture cure 2 Defects such as air holes and air bubbles on the surface or inside of the material can seriously affect the use appearance and mechanical properties of the material. CO removal by addition of antifoams or adsorbents 2 The gas effect is limited and the addition of these materials also reduces the usability and stability of the SPU material. The latent curing agent used in the SPU prepolymer can radically eliminate CO in the SPU material 2 And (4) generating. The curing mechanism of the (aldehyde) imine latent curing agent is shown as the following reaction formula:
R 1 -CH＝N-R-N＝CH-R 1 +2H 2 O→H 2 N-R-NH 2 +2R 1 CHO
latent curing process and use advantages of imine latent curing agent in one-component polyurethane material, patent CN107043447A and CN109251292A describe: because two amine groups are hidden, the imine has good fluidity at normal temperature, is very easy to mix with SPU, and has longer storage stability under the sealed and anhydrous condition; when the film is used, imine is preferentially mixed with H in the air 2 O reacts to generate primary amino, the primary amino is subjected to chain extension reaction with isocyanate group (NCO group) of SPU, and no CO is generated in the whole reaction process 2 The gas generation can prevent the SPU material from foaming, and simultaneously, the appearance and partial mechanical properties of the material are greatly improved.
Therefore, the development of a latent curing agent suitable for the SPU system becomes a hot spot in the research and development field of polyurethane curing agents at home and abroad at present.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects of the prior art and provide a latent curing agent suitable for an SPU system.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a cycloaliphatic imine latent curing agent comprises the following steps:
under the environment of nitrogen gas and air evacuation, 10-30 parts by weight of alicyclic primary amine and 0.5-5 parts by weight of catalyst A are mixed, stirred and heated to 40-120 ℃, then 5-30 parts by weight of aldehyde/ketone compound are dripped, and the heat preservation reaction is carried out for 6-15 hours;
standing the reaction solution for a certain time, removing water generated in the reaction, and filtering and recovering the catalyst A to obtain a crude product;
and (3) carrying out a stepped pressure-variable distillation mode combining atmospheric distillation and reduced pressure distillation on the crude product to recover excessive aldehyde/ketone compounds, and simultaneously distilling to remove water and other impurities to obtain the high-purity alicyclic imine latent curing agent.
In one embodiment of the present invention, the alicyclic primary amine is at least one of o-diamine methylcyclopentane, methylcyclopentamine, methylcyclohexanediamine, 1, 3-bis (aminomethyl) cyclohexane, isophoronediamine, and cyclohexylamine.
In one embodiment of the present invention, the aldehyde/ketone compound is at least one of acetone, butanone, pentanone, cyclohexanone, cyclopentanone, acetophenone, pinacolone, formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, n-butyraldehyde, benzaldehyde, salicylaldehyde, furfural, and cinnamaldehyde.
In one embodiment of the present invention, catalyst a is an acidic resin. For example, the acidic resin is at least one of zeolite solid acid, heteropoly acid solid acid, and cation exchange resin.
In one embodiment of the present invention, the molar ratio of the amino group of the alicyclic primary amine to the carbonyl group of the aldehyde/ketone compound is 1:1 to 1: 4; preferably, the molar ratio of amino groups to carbonyl groups is from 1:1.05 to 1: 1.25.
The invention also provides an alicyclic imine latent curing agent, which is prepared by the preparation method of the alicyclic imine latent curing agent; the cycloaliphatic imine latent curing agent.
The invention also provides a single-component polyurethane material, which comprises the following raw materials in parts by weight: 350 parts of oligomer polyol 250, 30-60 parts of polyisocyanate, 10-20 parts of imine latent curing agent, 2-5 parts of catalyst B and 2-6 parts of anti-aging agent; among them, the alicyclic imine latent curing agent of the present invention.
In one embodiment of the present invention, the oligomer polyol is at least one of polyoxypropylene glycol, polytetrahydrofuran glycol, tetrahydrofuran-propylene oxide copolyether, polyester polyol, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, polyacrylate polyol; preferably, the oligomer polyol used is at least one of polyoxypropylene diol, polytetrahydrofuran diol, polycaprolactone diol, polycarbonate diol.
In one embodiment of the present invention, the polyisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, and p-phenylene diisocyanate; preferably, the polyisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate.
In a specific embodiment of the invention, the catalyst B is at least one of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, triethylamine, and triethylenediamine.
In one embodiment of the invention, the anti-aging agent is at least one of antioxidant-264, antioxidant 1010, phenothiazine, light stabilizer UV-9, UV-24 and UV-328.
The invention adopts alicyclic primary amine and aldehyde/ketone compound as raw materials, and the alicyclic primary amine and aldehyde/ketone compound react under certain conditions to prepare the alicyclic imine latent curing agent. The cycloaliphatic imine latent curing agent can be applied to a single-component moisture curing polyurethane system, can solve the foaming problem of the polyurethane system in the moisture curing process, such as single-component polyurethane coating, single-component polyurethane adhesive, single-component polyurethane sealant and the like, and can also be applied to products such as a double-component polyurethane system and the like.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
Example 1
The embodiment provides a preparation method of an alicyclic imine latent curing agent, which comprises the following specific steps:
adding 128g of methylcyclohexanediamine and 5.5g of catalyst A (macroporous sulfonic acid type cation exchange resin) into a reaction kettle, introducing nitrogen to exhaust air in the kettle, stirring and heating to 70-85 ℃, then beginning to dropwise add 240g of pinacolone, and preserving heat at the temperature for reaction for 10 hours; after the heat preservation is finished, the feed liquid in the reaction kettle is kept stand and layered for 20 minutes, the water generated in the reaction is removed, and the crude imine product is obtained after the catalyst A is filtered and recovered; and then, carrying out a stepped pressure-variable distillation mode combining atmospheric distillation and reduced pressure distillation on the crude product to recover excessive pinacolone, and simultaneously distilling to remove other impurities to obtain colorless transparent liquid, wherein about 269g of the colorless transparent liquid is the cycloaliphatic imine latent curing agent.
The alicyclic imine is used as a latent curing agent and is applied to a single-component polyurethane material, and the formula of the single-component polyurethane material comprises the following raw materials in percentage by mass: 40% of polyether glycol PPG2000, 42% of polyether glycol PTMG2000, 12% of toluene diisocyanate (TDI-80), 4% of alicyclic imine latent curing agent, 0.8% of catalyst B dibutyltin dilaurate (T12) and 1.2% of antioxidant 1010.
The preparation method of the single-component polyurethane material comprises the following specific steps: adding PPG2000 and PTMG2000 into a three-neck flask according to the mass fraction in the formula, heating, stirring and dispersing uniformly, and dehydrating in vacuum for 1 hour at 105 ℃; when the temperature is reduced to 80 ℃, adding TDI-80 and catalyst B T12, and stirring for reaction for 3 hours; cooling to 60 ℃, adding the alicyclic imine latent curing agent and the antioxidant 1010, quickly stirring for 5 minutes, then defoaming in vacuum for 10 minutes, and filling nitrogen gas and sealing for later use.
Example 2
The embodiment provides a preparation method of an alicyclic imine latent curing agent, which comprises the following specific steps:
adding 170g of isophorone diamine and 8g of catalyst A (macroporous sulfonic acid type cation exchange resin) into a reaction kettle, introducing nitrogen to exhaust air in the kettle, stirring and heating to 40-55 ℃, then dropwise adding 173g of isobutyraldehyde, and carrying out heat preservation reaction for 12 hours at the temperature; after the heat preservation is finished, the feed liquid in the reaction kettle is kept stand and layered for 20 minutes, the water generated in the reaction is removed, and the crude imine product is obtained after the catalyst A is filtered and recovered; and then, carrying out a stepped pressure-variable distillation mode combining atmospheric distillation and reduced pressure distillation on the crude product to recover excessive isobutyraldehyde, and simultaneously distilling to remove other impurities to obtain colorless transparent liquid, wherein about 256g of the colorless transparent liquid is the alicyclic imine latent curing agent.
The alicyclic imine is used as a latent curing agent and is applied to a single-component polyurethane material, and the formula of the single-component polyurethane material comprises the following raw materials in percentage by mass: 35% of polyether glycol PPG2000, 45% of polyether glycol PTMG2000, 14% of diphenylmethane diisocyanate (liquefied MDI), 4% of alicyclic imine latent curing agent, 0.8% of catalyst B dibutyltin dilaurate (T12) and 1.2% of antioxidant 1010.
The preparation method of the single-component polyurethane material comprises the following specific steps: adding PPG2000 and PTMG2000 into a three-neck flask according to the mass fraction in the formula, heating, stirring, uniformly dispersing, and dehydrating in vacuum at 105 ℃ for 1 hour; cooling to 75 ℃, adding liquefied MDI and catalyst B T12, and stirring for reaction for 3 hours; cooling to 60 ℃, adding the alicyclic imine latent curing agent and the antioxidant 1010, quickly stirring for 5 minutes, then performing vacuum defoamation for 10 minutes, and filling nitrogen and sealing for later use.
Example 3
The embodiment provides a preparation method of an alicyclic imine latent curing agent, which comprises the following specific steps:
adding 142g of 1, 3-bis (aminomethyl) cyclohexane and 7g of macroporous sulfonic acid type cation exchange resin into a reaction kettle, introducing nitrogen to exhaust air in the kettle, stirring and heating to 40-50 ℃, then starting to dropwise add 165g of n-butyraldehyde, and carrying out heat preservation reaction for 8 hours at the temperature; after the heat preservation is finished, the feed liquid in the reaction kettle is kept stand and layered for 20 minutes, the water generated in the reaction is removed, and the crude imine product is obtained after the catalyst A is filtered and recovered; and then, carrying out a stepped pressure-variable distillation mode combining atmospheric distillation and reduced pressure distillation on the crude product to recover excessive n-butyraldehyde, and simultaneously distilling to remove other impurities to obtain colorless transparent liquid, wherein about 230g of the colorless transparent liquid is the alicyclic imine latent curing agent.
The alicyclic imine is used as a latent curing agent and is applied to a single-component polyurethane material, and the formula of the single-component polyurethane material comprises the following raw materials in percentage by mass: 43 percent of polyether glycol PPG2000, 43 percent of polyether glycol PTMG2000, 9 percent of isophorone diisocyanate (IPDI), 3 percent of alicyclic imine latent curing agent, 0.8 percent of catalyst B dibutyltin dilaurate (T12) and 1.2 percent of antioxidant 1010.
The preparation method of the single-component polyurethane material comprises the following specific steps: adding PPG2000 and PTMG2000 into a three-neck flask according to the mass fraction in the formula, heating, stirring and dispersing uniformly, and dehydrating in vacuum for 1 hour at 105 ℃; when the temperature is reduced to 85 ℃, IPDI and catalyst B T12 are added, and the mixture is stirred and reacts for 3 hours; cooling to 60 ℃, adding the alicyclic imine latent curing agent and the antioxidant 1010, quickly stirring for 5 minutes, then defoaming in vacuum for 10 minutes, and filling nitrogen gas and sealing for later use.
Example 4 (comparative example)
A single-component polyurethane material is used as a comparison sample, does not add alicyclic imine latent curing agent, and only relies on trace moisture in the air to carry out curing sample preparation. The formula of the single-component polyurethane material comprises the following raw materials in percentage by mass: 45% of polyether glycol PPG2000, 40% of polyether glycol PTMG2000, 13% of toluene diisocyanate (TDI-80), 0.8% of catalyst B dibutyltin dilaurate (T12) and 1.2% of antioxidant 1010.
The preparation method of the single-component polyurethane material comprises the following specific steps: adding PPG2000 and PTMG2000 into a three-neck flask according to the mass fraction in the formula, heating, stirring and dispersing uniformly, and dehydrating in vacuum for 1 hour at 105 ℃; when the temperature is reduced to 80 ℃, adding TDI-80 and catalyst B T12, and stirring for reaction for 3 hours; and (3) adding an antioxidant 1010 when the temperature is reduced to 60 ℃, quickly stirring for 5 minutes, then carrying out vacuum defoaming for 10 minutes, and filling nitrogen and sealing for later use.
Example 5 (comparative example)
This comparative example provides a cycloaliphatic imine latent curing agent that is essentially the same as example 1 except that: the consumption of the synthetic raw material methyl cyclohexanediamine is 130g, and the consumption of the pinacolone is 220 g; the catalyst A adopts macroporous sulfonic acid type cation exchange resin, and the addition amount is reduced to 4 g.
The cycloaliphatic imine prepared in this example was applied as a latent curing agent to a one-component polyurethane material, the formulation and amount of which and the method of preparation remained the same as in example 1.
Example 6 (comparative example)
This comparative example provides a cycloaliphatic imine latent curing agent that is essentially the same as example 1 except that: the dosage of the synthetic raw material, namely the methylcyclohexanediamine, is 140g, and the dosage of the pinacolone is 200 g; catalyst A used basic catalyst sodium methoxide, the addition was 7 g.
The cycloaliphatic imine prepared in this example was applied as a latent curing agent to a one-component polyurethane material, the formulation and amount of which and the method of preparation remained the same as in example 1.
The single-component polyurethane glues prepared in examples 1 to 6 were prepared by casting a glue sample having a thickness of about 1.5mm in a square mold in which a release agent was sprayed in advance, moisture-curing the glue sample at 25 ℃ under 50% relative humidity, and testing mechanical properties after curing for 7 days. The tensile strength and the elongation at break are tested according to the method of GB/T528-. The surface dry time was measured according to the method B of GB/T13477.5-2002, and the curing thickness 3 days after the gel sample preparation was measured according to the method II of GB/T32369-2015, to characterize the curing speed.
The results of the various tests are shown in table 1.
TABLE 1
| Serial number | Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| 1 | hardness/Shore A | 70 | 69 | 68 | 72 | 69 | 70 |
| 2 | Curing speed/mm | 2.69 | 2.57 | 2.61 | 1.83 | 2.31 | 1.97 |
| 3 | Surface drying time/h | 19 | 17 | 18 | 43 | 26 | 33 |
| 4 | Tensile strength/MPa | 14.57 | 14.08 | 14.33 | 12.46 | 13.65 | 12.88 |
| 5 | Elongation at break/% | 549 | 655 | 621 | 268 | 423 | 393 |
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a cycloaliphatic imine latent curing agent comprises the following steps:
under the environment of nitrogen gas and air evacuation, 10-30 parts by weight of alicyclic primary amine and 0.5-5 parts by weight of catalyst A are mixed, stirred and heated to 40-120 ℃, then 5-30 parts by weight of aldehyde/ketone compound are dripped, and the heat preservation reaction is carried out for 6-15 hours;
standing the reaction solution for a certain time, removing water generated by the reaction, and filtering and recovering the catalyst A to obtain a crude product;
and (3) carrying out a stepped pressure-variable distillation mode combining atmospheric distillation and reduced pressure distillation on the crude product to recover excessive aldehyde/ketone compounds, and simultaneously distilling to remove water and other impurities to obtain the high-purity alicyclic imine latent curing agent.
2. The production method according to claim 1, wherein the alicyclic primary amine is at least one of o-diaminomethylcyclopentane, methylcyclopentanediamine, methylcyclohexanediamine, 1, 3-bis (aminomethyl) cyclohexane, isophoronediamine, and cyclohexylamine.
3. The production method according to claim 1, wherein the aldehyde/ketone compound is at least one of acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, acetophenone, pinacolone, formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, n-butyraldehyde, benzaldehyde, salicylaldehyde, furfural, and cinnamaldehyde.
4. The production method according to claim 1, wherein the catalyst a is an acidic resin;
preferably, the acidic resin is at least one of zeolite solid acid, heteropoly acid solid acid and cation exchange resin.
5. The production method according to claim 1, wherein the molar ratio of the amino group of the alicyclic primary amine to the amino group/carbonyl group of the aldehyde/ketone compound is 1:1 to 1: 4.
6. A cycloaliphatic imine latent curing agent prepared by the preparation method according to any one of claims 1 to 5; the purity of the alicyclic imine latent curing agent is more than 95%.
7. The single-component polyurethane material comprises the following raw materials in parts by weight: 350 parts of oligomer polyol 250, 30-60 parts of polyisocyanate, 10-20 parts of imine latent curing agent, 2-5 parts of catalyst B and 2-6 parts of anti-aging agent;
wherein the latent hardener of the imine group is the latent hardener of the alicyclic imine group according to claim 6.
8. The one-component polyurethane material of claim 7, wherein the oligomer polyol is at least one of polyoxypropylene glycol, polytetrahydrofuran glycol, tetrahydrofuran-propylene oxide copolyether, polyester polyol, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, polyacrylate polyol.
9. The one-component polyurethane material of claim 7, wherein the polyisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, and p-phenylene diisocyanate.
10. The one-component polyurethane material of claim 7, wherein the catalyst B is at least one of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, triethylamine, triethylenediamine;
preferably, the anti-aging agent is at least one of antioxidant 264, antioxidant 1010, phenothiazine, light stabilizer UV-9, UV-24 and UV-328.
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| CN115974738A (en) * | 2022-09-01 | 2023-04-18 | 苏州湘园新材料股份有限公司 | Preparation method and application of aromatic imine latent curing agent |
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