CN117820651A - Preparation method of nonionic flexible epoxy curing agent - Google Patents
Preparation method of nonionic flexible epoxy curing agent Download PDFInfo
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- CN117820651A CN117820651A CN202410070402.2A CN202410070402A CN117820651A CN 117820651 A CN117820651 A CN 117820651A CN 202410070402 A CN202410070402 A CN 202410070402A CN 117820651 A CN117820651 A CN 117820651A
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- Prior art keywords
- curing agent
- epoxy
- nonionic
- flexible
- constant temperature
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 98
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims abstract description 77
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 238000001723 curing Methods 0.000 claims description 79
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 17
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 14
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000001361 adipic acid Substances 0.000 claims description 10
- 235000011037 adipic acid Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- YRZFHTRSHNGOSR-UHFFFAOYSA-N phenylmethanamine;trifluoroborane Chemical compound FB(F)F.NCC1=CC=CC=C1 YRZFHTRSHNGOSR-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 9
- 239000006184 cosolvent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 36
- 239000011248 coating agent Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 22
- 239000000839 emulsion Substances 0.000 description 16
- 239000003973 paint Substances 0.000 description 15
- 239000002966 varnish Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 229960001124 trientine Drugs 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- -1 chloride ions Chemical class 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 150000004072 triols Chemical group 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of epoxy curing agents, and particularly relates to a preparation method of a nonionic flexible epoxy curing agent. Adding polyether triol into water, uniformly stirring, adding a catalyst A for dissolution, heating, condensing and refluxing, introducing oxygen, and reacting at constant temperature to obtain a product A; after the product A is melted, adding a monofunctional epoxy reactive diluent, uniformly stirring, and adding a catalyst B for reaction to obtain a flexible intermediate; preheating a flexible intermediate, adding the preheated flexible intermediate into aliphatic polyamine, reacting at constant temperature, and distilling under reduced pressure to obtain a product B; and adding the epoxy resin solution into the product B for a first constant temperature reaction, adding the dibasic acid for a second constant temperature reaction, and adding deionized water to obtain the nonionic flexible epoxy curing agent. According to the invention, the hydrophilic group with a branched chain structure of the polyether triol is introduced, so that the curing agent has the advantages of excellent impact resistance, high flexibility and good water dispersibility, and can be stably dispersed in water without a cosolvent.
Description
Technical Field
The invention belongs to the technical field of epoxy curing agents, and particularly relates to a preparation method of a nonionic flexible epoxy curing agent.
Background
The epoxy resin is a thermoplastic high molecular linear polymer, has excellent adhesive force, acid and alkali resistance and good stability, and is widely used in the fields of paint, adhesive and the like. However, the uncured epoxy resin can soften and melt to become a viscous liquid state after being heated, and does not have good mechanical properties, chemical resistance and heat resistance. Therefore, a curing agent is required to be added for curing reaction, and the curing reaction is mainly based on the existence of active epoxy groups in the epoxy resin, and a three-dimensional network structure is formed by reaction with the curing agent, so that a high-molecular polymer with good performance is obtained. Therefore, the curing agent is a key for generating practical application value of the epoxy resin.
In recent years, as the damage of volatile organic compounds to human bodies and the environment is getting more and more attention, epoxy curing agents containing no or little organic volatile substances have become the focus of research on new epoxy. Currently, common waterborne epoxy curing agents are classified into cationic, anionic and nonionic curing agents according to chemical properties. The anionic aqueous epoxy resin curing agent is prepared by adding organic acid such as acetic acid and the like to react with polyamine to form salt, and overcomes the defects of low hydrophilicity, higher reaction activity, higher volatility, poor compatibility with epoxy resin and the like of fatty amine, but the organic acid added in the salt forming step can reduce the stability of the curing agent and react with a metal substrate, so that the corrosion resistance of a coating is reduced, and a cured paint film has higher brittleness and poor acid resistance. The pH value of the cationic aqueous epoxy curing agent is generally low, and the film forming property, the permeation resistance and the flexibility are poor, so that the application and popularization of the cationic aqueous epoxy curing agent in aqueous epoxy resin coatings are limited.
Chinese patent CN 104356357A discloses a method for synthesizing nonionic aqueous epoxy hardener, under the protection of dry nitrogen, propylene glycol methyl ether solution of triethylene tetramine is put into a 500ml four-port reaction bottle equipped with a reflux condenser, a thermometer and a stirrer; dropping polyether polyol diglycidyl ether, controlling the material dropping speed and the material molar ratio, and reacting to obtain triethylene tetramine and polyether polyol diglycidyl ether adduct; and (3) dropwise adding liquid epoxy resin into propylene glycol methyl ether solution of triethylene tetramine and polyether polyol diglycidyl ether adduct after residual triethylene tetramine is removed by reduced pressure distillation according to a stoichiometric ratio, and synthesizing to obtain the aqueous epoxy curing agent. The hydroxyl content of the polyether polyol diglycidyl ether adopted in the patent is not fixed, the reaction with the triethanolamine is difficult to control, and the explosion polymerization is extremely easy to cause crosslinking in the reaction process; the introduction of the propylene glycol methyl ether solvent can not effectively reduce the solvent content to ensure that the curing agent achieves zero VOC, and no amide group is introduced, so that the rheological property and the construction pot life performance of the coating can not be controlled better.
Chinese patent CN 106046325A discloses a water-based epoxy curing agent and a water-based epoxy vehicle frame paint, wherein the water-based epoxy curing agent is prepared from the following raw materials in parts by weight: 30-35 parts of triethylene tetramine, 1.2-1.7 parts of silane coupling agent, 8-12 parts of TMPEG, 0.1-0.4 part of epoxy resin, 8-13 parts of aromatic glycidyl ether and 0.03-0.07 part of nano alumina; the preparation method comprises the following steps: adding triethylene tetramine and a silane coupling agent into a reaction container according to the proportion, heating to 60 ℃ under the protection of nitrogen while stirring, then dropwise adding TMPEG, and preserving heat for 3-4 hours after dropwise adding to obtain an intermediate; adding epoxy resin into a reaction container, slowly dripping at 60 ℃ and reacting for 0.5-1 h to obtain an intermediate-epoxy adduct; then adding the aromatic glycidyl ether into a reaction container, reacting for 2-3 hours at 60 ℃, adding water to dilute until the solid content is 50%, and stirring for 0.5-1 hour; finally adding nano alumina, and stirring uniformly to obtain the aqueous epoxy curing agent. In the patent, an aminosilane coupling agent is adopted to participate in the reaction, the coupling efficiency is relatively low, and the durability is poor under the environments of high temperature, high humidity and the like; the curing agent prepared by the method is not suitable for recoating an intermediate coating or a finish paint on an upper layer, and is easy to cause the coating to fall off, so that the bonding effect between coating layers is poor; the addition of nano alumina is very prone to agglomeration and to emulsion breaking.
Disclosure of Invention
The invention aims to provide a preparation method of a nonionic flexible epoxy curing agent, which combines the advantages of water resistance and long construction application period of an amidated polyamine water-based epoxy curing agent, has the advantages of excellent impact resistance, high flexibility and good water dispersibility by introducing hydrophilic groups with branched structures into polyether triol, can be stably dispersed in water without a cosolvent, and has the advantage of low-temperature curing of an aliphatic curing agent, so that the water resistance of a coating is improved, and the method can be suitable for matching various emulsions/resins, thereby being beneficial to expanding the application field of the epoxy curing agent.
The preparation method of the nonionic flexible epoxy curing agent comprises the following steps:
(1) Adding polyether triol into water, stirring uniformly, adding a catalyst A for dissolution, heating, condensing and refluxing, introducing oxygen, reacting at constant temperature, performing first reduced pressure distillation, washing with a solvent, filtering to obtain clear liquid, and performing second reduced pressure distillation to obtain a product A;
(2) After the product A is melted, adding a monofunctional epoxy reactive diluent, uniformly stirring, and adding a catalyst B for reaction to obtain a flexible intermediate;
(3) Preheating a flexible intermediate, adding the preheated flexible intermediate into aliphatic polyamine, reacting at constant temperature, and distilling under reduced pressure to obtain a product B;
(4) And (3) dissolving epoxy resin in a solvent to obtain an epoxy resin solution, adding the epoxy resin solution into the product B to perform a first constant temperature reaction, adding diacid to perform a second constant temperature reaction, and adding deionized water to obtain the nonionic flexible epoxy curing agent.
The molecular weight of the polyether triol in the step (1) is 170-1000.
The mass ratio of the polyether triol to the water in the step (1) is 150-350:60-150.
The stirring temperature in the step (1) is 20-95 ℃.
The catalyst A in the step (1) is one or more of copper nitrate, ferric nitrate or potassium permanganate, and the mass of the catalyst A is 8-22% of the mass of polyether triol.
The temperature in the step (1) is raised to 100-150 ℃.
And (3) continuously introducing oxygen in the step (1), wherein the flow rate of the oxygen is 100-120ml/min.
The constant temperature reaction time in the step (1) is 4-8h.
The first reduced pressure distillation temperature in step (1) is 70-100 ℃.
The solvent in the step (1) is one or more of ethyl acetate, chloroform, methylene dichloride or isopropanol.
The second reduced pressure distillation temperature in the step (1) is 50-110 ℃.
The melting temperature in the step (2) is 90-140 ℃.
The monofunctional epoxy reactive diluent in the step (2) is one or more of phenyl glycidyl ether, butyl glycidyl ether or o-toluene glycidyl ether, and the molar ratio of the product A to the monofunctional epoxy reactive diluent is 1:0.8-1.3.
The catalyst B in the step (2) is one or more of tetraethylammonium bromide, tetrabutylammonium bromide, stannic chloride, boron trifluoride diethyl etherate or boron trifluoride benzylamine complex, and the mass of the catalyst B is 0.1-2% of the mass of the product A.
The reaction temperature in the step (2) is 90-140 ℃ and the epoxy equivalent is more than or equal to 10000g/eq.
The preheating temperature in the step (3) is 40-80 ℃.
The adding time in the step (3) is 1-2h.
The aliphatic polyamine in the step (3) is one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1, 5-pentanediamine or 2-methyl-1, 5-pentanediamine.
The reaction temperature in the step (3) is 130-190 ℃ and the reaction time is 3-6h.
The epoxy resin in the step (4) is one or more of bisphenol A type epoxy resins E-21, E-20, E-42, E-44 or E51.
The solvent in the step (4) is one or more of xylene, toluene, ethylene glycol propyl ether or ethylene glycol butyl ether.
The epoxy resin in the epoxy resin solution described in step (4) accounts for 60-90wt.%.
The mass ratio of the epoxy resin to the flexible intermediate in the step (4) is 60-160:120-230.
The adding time in the step (4) is 1-2h.
The first constant temperature reaction temperature in the step (4) is 60-120 ℃, and the first constant temperature reaction is carried out until the epoxy equivalent is more than or equal to 10000g/eq.
The dibasic acid in the step (4) is one or more of glutaric acid, adipic acid, terephthalic acid, azelaic acid or 1, 4-cyclohexanedicarboxylic acid, and the molar ratio of the epoxy resin to the dibasic acid is 8-15:1.
The second constant temperature reaction temperature in the step (4) is 130-190 ℃, and the second constant temperature reaction time is 2-5h.
The solid content of the nonionic flexible epoxy curing agent in the step (4) is 40-55%.
The preparation method of the nonionic flexible epoxy curing agent comprises the following specific steps:
(1) Adding polyether triol into water, stirring uniformly at 20-95 ℃, then adding a catalyst A for dissolving, heating to 100-150 ℃ after the materials are uniform, condensing and refluxing, introducing oxygen, reacting at constant temperature for 4-8h, performing first reduced pressure distillation at 70-100 ℃ for removing water, washing with a solvent, filtering to obtain clear liquid, and performing second reduced pressure distillation to obtain a product A (oxidizing triol into tricarboxylic acid);
(2) Melting the product A at 90-140 ℃, then adding a monofunctional epoxy reactive diluent, stirring uniformly, then adding a catalyst B, controlling the reaction temperature at 90-140 ℃, and reacting until the epoxy equivalent is more than or equal to 10000g/eq to obtain a Flexible Intermediate (FIMED);
(3) Heating FIMED to 40-80 ℃ and dropwise adding the FIMED into aliphatic polyamine, wherein the reaction temperature is 130-190 ℃, the dropwise adding time is controlled within 1-2h, and then reacting for 3-6h at constant temperature; then, distilling under reduced pressure to remove redundant aliphatic polyamine to obtain a product B;
(4) And (3) dissolving epoxy resin in a solvent to obtain an epoxy resin solution, dropwise adding the epoxy resin solution into the product B for 1-2h, then performing a first constant-temperature reaction at 60-120 ℃ until the epoxy equivalent is more than or equal to 10000g/eq, adding dibasic acid, performing a second constant-temperature reaction at 130-190 ℃ for 2-5h, and adding deionized water to ensure that the solid content is 40-55%, thereby obtaining the nonionic flexible epoxy curing agent.
The residual aliphatic polyamine is distilled off under reduced pressure in the step (3) and accounts for 60-85% of the total input amount of the aliphatic polyamine.
The total amine value of the nonionic flexible epoxy hardener prepared by the invention is 160-350mgKOH/g, and the active hydrogen equivalent is 220-450g/mol.
The invention synthesizes an intermediate with a polyether triol skeleton, improves the hydrophilic performance of the product by oxidizing alcohol into acid, and ensures that the product has certain hydrophilic capability. Compared with an intermediate prepared by adopting polyether glycol as a framework synthesis, the intermediate has a branched chain structure, and the structure is converted from a linear structure to a surface structure due to the existence of the branched chain, so that the intermediate has stronger flexibility and impact resistance when being applied to a coating. Meanwhile, the compactness of the molecular structure is improved by increasing the branched chain, the coating is more compact and has enhanced permeation resistance, and the water solubility of the curing agent is also considered, so that the coating is better combined with the epoxy emulsion, hydrophilic groups are not easy to migrate to the surface of the coating in the curing process, the water resistance of the coating is improved, and the coating is not easy to whiten. The invention does not introduce impurity ions such as chloride ions, is favorable for salt spray resistance of the coating, and can be better applied to the field of metal corrosion resistance.
The method introduces the diacid to react with the amine to reduce the content of primary amine, thereby prolonging the drying time of the curing agent and improving the rheological property, further improving the application period of the coating, improving the coating property and the glossiness of the coating, and ensuring that the curing agent is more beneficial to industrialized use. The introduced dibasic acid reacts with amine to obtain amide groups, so that the foam of the coating and the shrinkage of the coating can be effectively inhibited, the surface of the coating is smoother and smoother, and the appearance quality of the coating is improved.
The nonionic flexible epoxy curing agent prepared by the invention has good hydrophilic and lipophilic balance, can be dried at normal temperature (low temperature), and the coating prepared by the matched emulsion has good impact resistance, flexibility, water resistance and good anti-corrosion performance, does not contain an organic solvent, and can be matched with various emulsions/resins to be applied to multiple fields such as terraces, metal anti-corrosion and the like.
The beneficial effects of the invention are as follows:
(1) According to the invention, hydrophilic and oleophylic properties of the curing agent are adjusted by introducing hydrophilic chain segments such as polyether triol, aliphatic polyamine and the like into molecules; the polyol is oxidized into polybasic acid, so that the polybasic acid reacts with amine to generate amide groups, the hydrophilic performance of the curing agent is improved, the curing agent has good water solubility, and the coating prepared by mixing the curing agent and the epoxy emulsion has high compactness, excellent adhesive force (less than or equal to 1 level), water resistance 168h (30 d with partial matched paint), neutral salt fog resistance more than 500h and the like.
(2) The curing agent of the invention introduces polyether flexible chain segments such as polyether triol and the like into molecules, and the coating prepared by matching with the epoxy emulsion has super-strong flexibility of 1mm and impact resistance, and the impact resistance can reach 100kg cm.
(3) The curing agent disclosed by the invention does not introduce organic volatile matters, does not contain VOC, and has good environmental friendliness.
(4) The curing agent has mild preparation process conditions, is curable at normal temperature, improves the pot life of the curing agent by blocking through a monofunctional group, and reduces primary amine, water and CO 2 Is a side reaction of (a).
(5) The curing agent is a water-soluble curing agent, can be directly matched with various epoxy resins or emulsion, has strong emulsifying capacity and adaptability, can be cured at normal temperature, and can be applied to various fields according to different emulsions/resins.
Detailed Description
The invention is further described below with reference to examples.
The performance of the nonionic flexible epoxy curing agent prepared in the invention is characterized by adopting the following method and standard:
solid content test of curing agent: testing was performed according to the GBT1725-2007 "determination of non-volatile content of paints, varnishes and plastics";
viscosity testing of the curing agent was determined using a Brookfield rotational viscometer DV 2T;
coating performance test: the tin plate is used for testing the drying time, impact resistance, flexibility and adhesive force, and the thickness of a paint film is 23+/-3 mu m; other tests used a Q215 steel plate with a coating thickness of 40±5 μm;
the paint film performance test was performed as follows:
drying time: testing according to GBT1728-2020 'paint film, putty film drying time measurement method';
impact resistance: testing was performed according to GB/T1732-2020 "paint film impact resistance assay" specifications;
flexibility: testing according to the specification of GBT1731-2020 'paint film putty film flexibility measuring method';
adhesion force: testing was performed as specified by GBT9286-2021 "paint and varnish cross-hatch test";
hardness: the test was carried out according to the GBT6739-2006 "paint film hardness measured by the paint and varnish pencil method" specification;
water resistance: testing was performed as specified in GB/T1733-1993 under the A-code;
acid resistance: testing was performed as specified in GB/T9274-1988 under the A-code;
alkali resistance: testing was performed as specified in GB/T9274-1988 under the A-code;
neutral salt spray resistance: the test was performed according to the GBT1771-2007 "determination of neutral salt spray resistance of paints and varnishes".
Example 1
(1) Adding 350g of polyether triol (with the molecular weight of 700) into a 1000ml four-neck flask, heating in an oil bath at the temperature of 60 ℃, adding 150g of water, stirring uniformly, adding 49g of ferric nitrate nonahydrate and 26g of potassium permanganate, dissolving, heating to 130 ℃ after the materials are uniform, condensing and refluxing, introducing oxygen, reacting at the constant temperature for 6 hours, distilling at the temperature of 90 ℃ under reduced pressure for removing water for the first time, washing with isopropanol and dichloromethane, filtering to obtain clear liquid, and distilling at the temperature of 90 ℃ under reduced pressure for the second time to obtain a product A;
(2) 375g of a product A is added into a 500ml four-neck flask, melted at 120 ℃, 82g of o-toluene glycidyl ether is added, 0.46g of tetrabutylammonium bromide serving as a catalyst is added after uniform stirring, the reaction temperature is controlled at 120 ℃, and the reaction is carried out until the epoxy equivalent is more than or equal to 10000g/eq, so as to obtain a Flexible Intermediate (FIMED);
(3) Heating 228.5g of FIMED to 60 ℃ and dropwise adding the FIMED into a 1000ml four-neck flask containing 435g of triethylene tetramine, adjusting the reaction temperature to 180 ℃, dropwise adding the FIMED for 1.5h, and then reacting at constant temperature for 4.5h; then, the excess triethylene tetramine (347.3 g) is distilled off under reduced pressure to obtain a product B;
(4) 145.5g of epoxy resin E21 is taken and dissolved in dimethylbenzene to obtain an epoxy resin solution (80 wt.% of the epoxy resin E21), the epoxy resin solution is dripped into a product B for 1.5h, then the epoxy resin solution is subjected to a first constant temperature reaction at 80 ℃ until the epoxy equivalent is more than or equal to 10000g/eq, then 2.3g of adipic acid is added, a second constant temperature reaction at 180 ℃ is carried out for 4h, and then deionized water is added, so that the nonionic flexible epoxy curing agent is obtained.
Example 2
(1) Adding 225g of polyether triol (with the molecular weight of 450) into a 500ml four-neck flask, heating in an oil bath at 70 ℃, adding 100g of water, stirring uniformly, adding 12.6g of cupric nitrate trihydrate and 18g of potassium permanganate for dissolving, heating to 130 ℃ after the materials are uniform, condensing and refluxing, introducing oxygen, reacting at constant temperature for 8 hours, distilling at 90 ℃ for water removal under reduced pressure for the first time, washing with isopropanol and dichloromethane, filtering to obtain clear liquid, and distilling at 90 ℃ for the second time under reduced pressure to obtain a product A;
(2) 249g of a product A is added into a 500ml four-neck flask, the mixture is melted at 120 ℃, 65g of o-toluene glycidyl ether is added, 0.49g of tetraethylammonium bromide serving as a catalyst is added after uniform stirring, the reaction temperature is controlled at 120 ℃, and the reaction is carried out until the epoxy equivalent is more than or equal to 10000g/eq, so as to obtain a Flexible Intermediate (FIMED);
(3) Heating 157g of FIMED to 60 ℃ and dropwise adding the mixture into a 1000ml four-neck flask containing 410g of triethylene tetramine, adjusting the reaction temperature to 180 ℃, dropwise adding the mixture for 1.5h, and then reacting at constant temperature for 4.5h; then, the excess triethylene tetramine (329.6 g) is distilled off under reduced pressure to obtain a product B;
(4) 156.3g of epoxy resin E20 is taken and dissolved in dimethylbenzene to obtain an epoxy resin solution (80 wt.% of the epoxy resin E20), the epoxy resin solution is dripped into a product B for 1.5h, then the epoxy resin solution is subjected to a first constant temperature reaction at 80 ℃ until the epoxy equivalent is more than or equal to 10000g/eq, then 4.5g of adipic acid is added, a second constant temperature reaction at 180 ℃ is carried out for 4h, and then deionized water is added, so that the nonionic flexible epoxy curing agent is obtained.
Example 3
(1) 150g of polyether triol (with the molecular weight of 300) is added into a 500ml four-neck flask, oil bath heating is carried out at the temperature of 55 ℃,60 g of water is added, stirring is carried out uniformly, then 16g of ferric nitrate nonahydrate and 14g of potassium permanganate are added for dissolution, the temperature is raised to 130 ℃ after the materials are uniform, condensation reflux is carried out, oxygen is introduced, the constant temperature reaction is carried out for 8 hours, the first reduced pressure distillation at the temperature of 90 ℃ is carried out for water removal, then isopropanol and methylene dichloride are used for washing, the clear liquid is obtained after filtration, and the second reduced pressure distillation at the temperature of 100 ℃ is carried out, thus obtaining a product A;
(2) Adding 175.5g of a product A into a 500ml four-neck flask, melting at 90 ℃, then adding 65g of butyl glycidyl ether, uniformly stirring, adding 0.49g of tetraethylammonium bromide serving as a catalyst, controlling the reaction temperature at 100 ℃, and reacting until the epoxy equivalent is more than or equal to 10000g/eq to obtain a Flexible Intermediate (FIMED);
(3) Heating 120.3g FIMED to 60 ℃ and dropwise adding the FIMED into a 1000ml four-neck flask containing 410g triethylene tetramine, adjusting the reaction temperature to 170 ℃, dropwise adding for 1.5h, and then reacting at constant temperature for 4.5h; then, the excess triethylene tetramine (329.6 g) is distilled off under reduced pressure to obtain a product B;
(4) 156.3g of epoxy resin E20 is taken and dissolved in dimethylbenzene to obtain an epoxy resin solution (80 wt.% of the epoxy resin E20), the epoxy resin solution is dripped into a product B for 1.5h, then the epoxy resin solution is subjected to a first constant temperature reaction at 90 ℃ until the epoxy equivalent is more than or equal to 10000g/eq, then 4.6g of adipic acid is added, a second constant temperature reaction at 180 ℃ is carried out for 4h, and then deionized water is added, so that the nonionic flexible epoxy curing agent is obtained.
Example 4
(1) 150g of polyether triol (with the molecular weight of 300) is added into a 500ml four-neck flask, the mixture is heated in an oil bath at the temperature of 60 ℃,60 g of water is added and stirred uniformly, then 16g of cupric nitrate trihydrate and 14g of potassium permanganate are added for dissolution, the temperature is raised to 150 ℃ after the materials are uniform, the mixture is condensed and refluxed, oxygen is introduced, the mixture reacts at the constant temperature for 4 hours, water is distilled and removed at the temperature of 100 ℃ under reduced pressure for the first time, then isopropanol and methylene dichloride are used for washing, clear liquid is obtained after filtration, and the second distillation under reduced pressure at the temperature of 80 ℃ is carried out, thus obtaining a product A;
(2) Adding 175.5g of a product A into a 500ml four-neck flask, melting at 100 ℃, then adding 82g of o-toluene glycidyl ether, uniformly stirring, adding 0.49g of tetrabutylammonium bromide serving as a catalyst, controlling the reaction temperature at 120 ℃, and reacting until the epoxy equivalent is more than or equal to 10000g/eq to obtain a Flexible Intermediate (FIMED);
(3) Heating 128.8g of FIMED to 70 ℃ and dropwise adding the FIMED into a 500ml four-neck flask containing 325.8g of 2-methyl-1, 5-pentanediamine, adjusting the reaction temperature to 170 ℃, dropwise adding the FIMED for 2 hours, and then reacting at constant temperature for 3.5 hours; subsequently, 253.8g of excess 2-methyl-1, 5-pentanediamine was distilled off under reduced pressure to obtain a product B;
(4) 71g of epoxy resin E44 is taken and dissolved in dimethylbenzene to obtain an epoxy resin solution (80 wt.% of the epoxy resin E44), the epoxy resin solution is dripped into a product B for 2 hours, then the epoxy resin is subjected to a first constant temperature reaction at 100 ℃ until the epoxy equivalent is more than or equal to 10000g/eq, then 2.3g of adipic acid is added, a second constant temperature reaction at 190 ℃ is carried out for 4 hours, and then deionized water is added, so that the nonionic flexible epoxy curing agent is obtained.
Example 5
(1) 150g of polyether triol (with the molecular weight of 300) is added into a 500ml four-neck flask, the mixture is heated in an oil bath at the temperature of 60 ℃,60 g of water is added and stirred uniformly, then 16g of ferric nitrate nonahydrate and 14g of potassium permanganate are added for dissolution, the temperature is raised to 100 ℃ after the materials are uniform, the mixture is condensed and refluxed, oxygen is introduced, the mixture reacts at the constant temperature for 8 hours, water is distilled and removed at the temperature of 70 ℃ under reduced pressure for the first time, then isopropanol and methylene dichloride are used for washing, clear liquid is obtained after filtration, and the second distillation under reduced pressure at the temperature of 100 ℃ is carried out, thus obtaining a product A;
(2) Adding 175.5g of a product A into a 500ml four-neck flask, melting at 120 ℃, then adding 82g of o-toluene glycidyl ether, uniformly stirring, adding 0.49g of tetrabutylammonium bromide serving as a catalyst, controlling the reaction temperature at 140 ℃, and reacting until the epoxy equivalent is more than or equal to 10000g/eq to obtain a Flexible Intermediate (FIMED);
(3) Heating 128.8g of FIMED to 80 ℃ and dropwise adding the FIMED into a 500ml four-neck flask containing 284 g of 1, 5-pentanediamine, adjusting the reaction temperature to 170 ℃, dropwise adding for 1h, and then reacting at constant temperature for 4h; then, 231.2g of excess 1, 5-pentanediamine was distilled off under reduced pressure to obtain a product B;
(4) 61.4g of epoxy resin E51 is taken and dissolved in dimethylbenzene to obtain an epoxy resin solution (80 wt.% of the epoxy resin E51), the epoxy resin solution is dripped into a product B for 1.5h, then the epoxy resin solution is subjected to a first constant temperature reaction at 80 ℃ until the epoxy equivalent is more than or equal to 10000g/eq, then 30.1g of adipic acid is added, a second constant temperature reaction at 160 ℃ is carried out for 5h, and then deionized water is added, so that the nonionic flexible epoxy curing agent is obtained.
Comparative example 1
(1) Adding 157.5g of polyether glycol (molecular weight is 315) into a 500ml four-neck flask, heating in an oil bath at 60 ℃, adding 60g of water, stirring uniformly, adding 12g of ferric nitrate nonahydrate and 10g of potassium permanganate, dissolving, heating to 130 ℃ after the materials are uniform, condensing and refluxing, introducing oxygen, reacting at constant temperature for 8 hours, distilling at 90 ℃ for the first time under reduced pressure to remove water, washing with isopropanol and dichloromethane, filtering to obtain clear liquid, and performing second reduced pressure distillation to obtain a product a (oxidizing the glycol into dicarboxylic acid);
(2) Adding 175.5g of a product a into a 500ml four-neck flask, melting at 120 ℃, then adding 41g of o-toluene glycidyl ether, uniformly stirring, adding 0.49g of tetrabutylammonium bromide serving as a catalyst, controlling the reaction temperature at 120 ℃, and reacting until the epoxy equivalent is more than or equal to 10000g/eq to obtain an intermediate;
(3) 200g of intermediate is heated to 60 ℃ and is dripped into a 500ml four-neck flask containing 300g of 1, 5-pentanediamine, the reaction temperature is adjusted to 170 ℃, the dripping time is 1.5 hours, and then the constant temperature reaction is carried out for 4.5 hours; then, 221g of redundant 1, 5-pentanediamine is distilled off under reduced pressure to obtain a product b;
(4) 72g of epoxy resin E51 is taken and dissolved in dimethylbenzene to obtain an epoxy resin solution (80 wt.% of the epoxy resin E51), the epoxy resin solution is dripped into the product b for 1.5h, then the epoxy resin is reacted at the first constant temperature of 80 ℃ until the epoxy equivalent is more than or equal to 10000g/eq, then 26g of adipic acid is added, the second constant temperature of 180 ℃ is reacted for 4h, and then deionized water is added to obtain the curing agent.
Comparative example 2
(1) 150g of polyether triol (with the molecular weight of 300) is added into a 500ml four-neck flask, the mixture is heated in an oil bath at the temperature of 60 ℃,60 g of water is added and stirred uniformly, then 16g of ferric nitrate nonahydrate and 14g of potassium permanganate are added for dissolution, the temperature is raised to 100 ℃ after the materials are uniform, the mixture is condensed and refluxed, oxygen is introduced, the mixture reacts at the constant temperature for 8 hours, water is distilled and removed at the temperature of 70 ℃ under reduced pressure for the first time, then isopropanol and methylene dichloride are used for washing, clear liquid is obtained after filtration, and the second distillation under reduced pressure at the temperature of 100 ℃ is carried out, thus obtaining a product A;
(2) Adding 175.5g of a product A into a 500ml four-neck flask, melting at 120 ℃, then adding 82g of o-toluene glycidyl ether, uniformly stirring, adding 0.49g of tetrabutylammonium bromide serving as a catalyst, controlling the reaction temperature at 140 ℃, and reacting until the epoxy equivalent is more than or equal to 10000g/eq to obtain a Flexible Intermediate (FIMED);
(3) Heating 128.8g of FIMED to 80 ℃ and dropwise adding the FIMED into a 500ml four-neck flask containing 284 g of 1, 5-pentanediamine, adjusting the reaction temperature to 170 ℃, dropwise adding for 1h, and then reacting at constant temperature for 4h; then, 231.2g of excess 1, 5-pentanediamine was distilled off under reduced pressure to obtain a product B;
(4) 61.4g of epoxy resin E51 is taken and dissolved in xylene to obtain an epoxy resin solution (80 wt.% of epoxy resin E51), the epoxy resin solution is dripped into a product B for 1.5h, then the mixture is reacted at a constant temperature of 80 ℃ until the epoxy equivalent is more than or equal to 10000g/eq, and then deionized water is added to obtain the curing agent.
The performance parameters of the curing agents prepared in examples 1-5 and comparative examples 1-2 are shown in Table 1.
Application example 1
The nonionic flexible epoxy curing agent prepared in the above example 1 was mixed with liquid epoxy resin E-51 (epoxy equivalent 196 g/eq) in a molar ratio of epoxy group to amino hydrogen of 1:0.8, and then diluted with water to a system solid content of 40%, to obtain a two-component waterborne epoxy resin varnish, which was applied to a test panel by brushing and coating.
Application example 2
Mixing the nonionic flexible epoxy curing agent prepared in the embodiment 2 with epoxy emulsion Ancare AR555 (epoxy equivalent 1300 g/eq) according to the molar ratio of epoxy groups to amino hydrogens of 1:0.8, adding water to dilute the mixture until the solid content of the system is 40%, and obtaining the two-component waterborne epoxy resin varnish, and coating the two-component waterborne epoxy resin varnish on a test board by using a coating machine to prepare a coated board.
Application example 3
Mixing the nonionic flexible epoxy curing agent prepared in the above example 3 with epoxy emulsion Ancare AR555 (epoxy equivalent 1300 g/eq) according to the molar ratio of epoxy groups to amino hydrogens of 1:0.8, then adding water to dilute to the system solid content of 40%, and obtaining the two-component waterborne epoxy resin varnish, and coating the two-component waterborne epoxy resin varnish on a test board by using a coating machine to prepare a coated board.
Application example 4
Mixing the nonionic flexible epoxy curing agent prepared in the above example 4 with epoxy emulsion Ancare AR555 (epoxy equivalent 1300 g/eq) according to the molar ratio of epoxy groups to amino hydrogens of 1:0.8, adding water to dilute to the system solid content of 40%, obtaining a two-component waterborne epoxy resin varnish, and coating the two-component waterborne epoxy resin varnish on a test board by using a coating machine to prepare a coated board.
Application example 5
Mixing the nonionic flexible epoxy curing agent prepared in the above example 5 with epoxy emulsion Ancare AR555 (epoxy equivalent 1300 g/eq) according to the molar ratio of epoxy groups to amino hydrogens of 1:0.8, adding water to dilute to the system solid content of 40%, obtaining a two-component waterborne epoxy resin varnish, and coating the two-component waterborne epoxy resin varnish on a test board by using a coating machine to prepare a coated board.
Application example 6
The curing agent prepared in the comparative example 1 is mixed with epoxy emulsion Ancarez AR555 (epoxy equivalent 1300 g/eq) according to the molar ratio of epoxy group to amino hydrogen of 1:0.8, water is added for dilution until the solid content of the system is 40%, and the two-component waterborne epoxy resin varnish is obtained and is coated on a test plate by a brushing method.
Application example 7
The curing agent prepared in the comparative example 2 is mixed with epoxy emulsion Ancarez AR555 (epoxy equivalent 1300 g/eq) according to the mole ratio of epoxy group to amino hydrogen of 1:0.8, water is added for dilution until the solid content of the system is 40%, and the two-component waterborne epoxy resin varnish is obtained and is coated on a test plate by a brushing method.
Application example 1 is applied to the field of floors, and application examples 2-7 are applied to metal corrosion prevention. The results of the coating performance tests (maintenance at 23.+ -. 2 ℃ C. For 7 days after curing) prepared in application examples 1-7 are shown in Table 2.
As can be seen from Table 2, the products prepared using the nonionic flexible epoxy curing agents of the present invention have excellent flexibility and impact resistance. Comparative application example 6 the product produced by the curing agent prepared from polyether glycol, application examples 1-5 have significant advantages in properties such as flexibility, impact resistance, alkali resistance, neutral salt spray resistance, etc. Comparative application example 7 the introduction of adipic acid in application examples 1-5 provides a significant advantage in pot life of the coating, for products produced without the addition of a curing agent prepared from adipic acid. According to application examples 1-5, different resins/emulsions can be selected to be applied to the field of epoxy terrace/metal corrosion prevention.
Claims (10)
1. The preparation method of the nonionic flexible epoxy curing agent is characterized by comprising the following steps:
(1) Adding polyether triol into water, stirring uniformly, adding a catalyst A for dissolution, heating, condensing and refluxing, introducing oxygen, reacting at constant temperature, performing first reduced pressure distillation, washing with a solvent, filtering to obtain clear liquid, and performing second reduced pressure distillation to obtain a product A;
(2) After the product A is melted, adding a monofunctional epoxy reactive diluent, uniformly stirring, and adding a catalyst B for reaction to obtain a flexible intermediate;
(3) Preheating a flexible intermediate, adding the preheated flexible intermediate into aliphatic polyamine, reacting at constant temperature, and distilling under reduced pressure to obtain a product B;
(4) And (3) dissolving epoxy resin in a solvent to obtain an epoxy resin solution, adding the epoxy resin solution into the product B to perform a first constant temperature reaction, adding diacid to perform a second constant temperature reaction, and adding deionized water to obtain the nonionic flexible epoxy curing agent.
2. The method for preparing a nonionic flexible epoxy curing agent according to claim 1, wherein the molecular weight of the polyether triol in the step (1) is 170-1000, and the mass ratio of the polyether triol to water is 150-350:60-150.
3. The method for preparing the nonionic flexible epoxy curing agent according to claim 1, wherein the stirring temperature in the step (1) is 20-95 ℃, the catalyst A is one or more of copper nitrate, ferric nitrate or potassium permanganate, the mass of the catalyst A is 8-22% of the mass of polyether triol, the temperature is raised to 100-150 ℃, the constant temperature reaction time is 4-8 hours, the first reduced pressure distillation temperature is 70-100 ℃, the solvent is one or more of ethyl acetate, chloroform, dichloromethane or isopropanol, and the second reduced pressure distillation temperature is 50-110 ℃.
4. The method for preparing a nonionic flexible epoxy curing agent according to claim 1, wherein the melting temperature in the step (2) is 90-140 ℃.
5. The method for preparing the nonionic flexible epoxy curing agent according to claim 1, wherein the monofunctional epoxy reactive diluent in the step (2) is one or more of phenyl glycidyl ether, butyl glycidyl ether and o-toluene glycidyl ether, and the molar ratio of the product A to the monofunctional epoxy reactive diluent is 1:0.8-1.3.
6. The method for preparing the nonionic flexible epoxy curing agent according to claim 1, wherein the catalyst B in the step (2) is one or more of tetraethylammonium bromide, tetrabutylammonium bromide, stannic chloride, boron trifluoride diethyl ether complex or boron trifluoride benzylamine complex, the mass of the catalyst B is 0.1-2% of the mass of the product A, the reaction temperature is 90-140 ℃, and the reaction is carried out until the epoxy equivalent is more than or equal to 10000g/eq.
7. The method for preparing the nonionic flexible epoxy curing agent according to claim 1, wherein the preheating temperature in the step (3) is 40-80 ℃, the adding time is 1-2h, the aliphatic polyamine is one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1, 5-pentanediamine or 2-methyl-1, 5-pentanediamine, the reaction temperature is 130-190 ℃, and the reaction time is 3-6h.
8. The method for preparing a nonionic flexible epoxy curing agent according to claim 1, wherein the epoxy resin in the step (4) is one or more of bisphenol a type epoxy resins E-21, E-20, E-42, E-44 or E51, the solvent is one or more of xylene, toluene, ethylene glycol propyl ether or ethylene glycol butyl ether, the epoxy resin in the epoxy resin solution accounts for 60-90wt.%, and the mass ratio of the epoxy resin to the flexible intermediate is 60-160:120-230.
9. The method for preparing the nonionic flexible epoxy curing agent according to claim 1, wherein the adding time in the step (4) is 1-2h, the first constant temperature reaction temperature is 60-120 ℃, the first constant temperature reaction is carried out until the epoxy equivalent is more than or equal to 10000g/eq, the diacid is one or more of glutaric acid, adipic acid, terephthalic acid, azelaic acid or 1,4 cyclohexane dicarboxylic acid, the molar ratio of epoxy resin to diacid is 8-15:1, the second constant temperature reaction temperature is 130-190 ℃, and the second constant temperature reaction time is 2-5h.
10. The method for preparing the nonionic flexible epoxy curing agent according to claim 1, wherein the solid content of the nonionic flexible epoxy curing agent in the step (4) is 40-55%.
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