CN106397780B - Preparation method of functional epoxy resin curing agent - Google Patents
Preparation method of functional epoxy resin curing agent Download PDFInfo
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- CN106397780B CN106397780B CN201610821180.9A CN201610821180A CN106397780B CN 106397780 B CN106397780 B CN 106397780B CN 201610821180 A CN201610821180 A CN 201610821180A CN 106397780 B CN106397780 B CN 106397780B
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- epoxy resin
- preparation
- curing agent
- polyethylene polyamine
- silicon
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 85
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 45
- -1 monoepoxy glycidyl Chemical group 0.000 claims abstract description 33
- 239000004698 Polyethylene Substances 0.000 claims abstract description 32
- 229920000768 polyamine Polymers 0.000 claims abstract description 32
- 229920000573 polyethylene Polymers 0.000 claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000004814 polyurethane Substances 0.000 claims description 25
- 229920002635 polyurethane Polymers 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 23
- 238000007789 sealing Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 150000002334 glycols Chemical class 0.000 claims description 11
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 7
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- HCPAOTGVQASBMP-UHFFFAOYSA-N 2-(oxiran-2-ylmethyl)oxirane Chemical compound C1OC1CC1CO1 HCPAOTGVQASBMP-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- 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
- 150000007524 organic acids Chemical class 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 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
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 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 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 2
- 229920002545 silicone oil Polymers 0.000 abstract description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract 3
- 150000002009 diols Chemical class 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 10
- 229920006334 epoxy coating Polymers 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000010721 machine oil Substances 0.000 description 5
- 125000005474 octanoate group Chemical group 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G59/50—Amines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a functional epoxy resin curing agent, which comprises the steps of firstly, reacting diisocyanate, polyether diol and hydroxyl silicone oil to prepare a silicon-containing end isocyanate group-containing polyurethane prepolymer, then adding epoxy resin E-51, and continuing to react to prepare silicon-containing polyurethane prepolymer grafted epoxy resin; then dripping monoepoxy glycidyl ether into polyethylene polyamine to prepare single-end-capped polyethylene polyamine; finally, the epoxy resin grafted by the silicon-containing polyurethane prepolymer is dripped into the single-end-capped polyethylene polyamine to react to obtain the tough heat-resistant water-based epoxy resin curing agent. The curing agent prepared by the invention has moderate amine equivalent, can emulsify and cure low molecular weight epoxy resin, is nontoxic and harmless, and greatly improves the toughness, heat resistance and water resistance of a curing film prepared by curing the epoxy resin.
Description
One, technical field
The present invention relates to a kind of preparation method of curing agent, specifically a kind of system of functional epoxy resin curing agent
Preparation Method belongs to curing agent technology field.
Two, background technique
Epoxy resin is widely used in the fields such as building, chemical industry, traffic, electronics, and product is mainly based on solvent type, largely
The use of organic solvent can cause very big harm to environment.Though there is good cementability, insulating properties and excellent antiseptic property,
But the disadvantages of there is also toughness and poor impact resistances is subject to certain restrictions its application.Therefore, to epoxy resin roughening and aqueous
The research of change has great importance.
Introduce that soft segment is epoxy resin toughened has a clear superiority than additional toughener in curing agent.Polyurethane has light
The advantages that damp degree is good, elastic high, bonding force is strong, can be modified toughened epoxy resin in many ways in conjunction with epoxy resin
Effective ways.But polyurethane toughened epoxy resin will cause the reduction of system heat resistance, and organosilicon has unique chemistry knot
Structure, surface can be lower, can assign polymer-modified film excellent water-fast, resistance in film forming procedure to surface enrichment
The performances such as time, resistance to greasy dirt and high-low temperature resistant.Organosilicon and polyurethane structural are introduced simultaneously in curing agent, with epoxy resin
Toughness, the heat resistance water resistance for solidifying prepared epoxy resin cure film are improved.
Three, summary of the invention
The present invention is intended to provide a kind of preparation method of functional epoxy resin curing agent, curing agent of the present invention can be newborn simultaneously
Change and cured epoxy resin, and can be improved the toughness, heat resistance and water resistance of epoxy resin.
The preparation method of functional epoxy resin curing agent of the present invention, includes the following steps:
(1) preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
Polyether Glycols heating is vacuumized, is dehydrated 2.0 hours in 120 DEG C, is then cooled to 50 DEG C, hydroxy silicon oil is added
And diisocyanate, control-NCO and-OH molar ratio are 2.0-3.0:1.0, and the mole of hydroxyl is with polyether Glycols and hydroxyl
The mass ratio of total hydroxyl meter of silicone oil, hydroxy silicon oil and polyether Glycols is 1:1.5-3, under the action of catalyst in 50-90 DEG C
Epoxy resin E-51 is then added in reaction 1.5-2.5 hours, and being warming up to 70-95 DEG C, the reaction was continued 2-3 hours, obtains siliceous poly-
The epoxy resin of urethane performed polymer grafting；
The number-average molecular weight of the polyether Glycols is 400-4000.
The diisocyanate is toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate (IPDI), hexa-methylene
Diisocyanate (HDI) or methyl diphenylene diisocyanate (MDI).
The hydroxy silicon oil is small-molecular-weight hydroxy silicon oil, molecular weight 800-900.
The catalyst is dibutyl tin dilaurate or stannous octoate, and additive amount is polyether Glycols, diisocyanate
With the 0.2-0.4% of epoxy resin E-51 gross mass.
The additive amount of the epoxy resin E-51 is polyether Glycols, diisocyanate and epoxy resin E-51 gross mass
45-60%.
(2) preparation of single sealing end polyethylene polyamine
Single glycidyl oxirane is slowly added dropwise into polyethylene polyamine, single glycidyl oxirane and polyethylene polyamine
Molar ratio be 1:1, react 3-4 hour at 60-80 DEG C, obtain singly block polyethylene polyamine；
The list glycidyl oxirane is butyl glycidyl ether, phenyl glycidyl ether, C12-14In glycidol ether
Any one or a few.
The polyethylene polyamine is m-phenylene diamine (MPD), diethylenetriamine, triethylene tetramine or tetraethylenepentamine.
(3) preparation of functional epoxy resin curing agent
Epoxy resin and solvent that silicon-based polyurethane performed polymer is grafted are added dropwise in single sealing end polyethylene polyamine, wherein controlling
Epoxy group processed and the molar ratio of single sealing end polyethylene polyamine are 1:1-1.5, are reacted 3-4 hours at 60-80 DEG C, being then added has
Machine acid is at salt, and the molar ratio of organic acid and remaining amine hydrogen is 1:4-5, and the reaction was continued at 55-65 DEG C 0.5-1 hours, reaction knot
Vacuum distillation removes solvent after beam, and deionized water is added, and aqueous epoxy resin curing agent is made, and solid content is controlled in 45-55%.
The organic acid is acetic acid or oxalic acid.
The solvent is one or more of propylene glycol monomethyl ether, propylene-glycol ethyl ether, ethylene glycol ethyl ether.
Compared with prior art, the invention has the following advantages that
1, curing agent of the present invention has good emulsification to liquid epoxies, and is curable epoxy tree under room temperature
Rouge.
2, the present invention prepares the poly- ammonia of siliceous terminal isocyanate group first with polyether Glycols, diisocyanate and hydroxy silicon oil
Ester performed polymer, then Graft Epoxy Resin prepares the epoxy resin of silicon-based polyurethane performed polymer grafting, the heat-resisting water of preparation toughness
Property epoxy curing agent, while polyurethane and organosilicon structures are introduced, the toughness of cured film can either be improved, and can improve
The heat resistance and water resistance of cured film.
Four, specific embodiment
Embodiment 1:
In the present embodiment functional epoxy resin curing agent the preparation method is as follows:
1, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
35g polyethers N210 is added in dry four-hole boiling flask, dehydration 2.0 hours is vacuumized at 120 DEG C, is then cooled down
To 50 DEG C, 12.6g hydroxy silicon oil and 22.2g IPDI is added, reacts 2 in 90 DEG C under octoate catalyst stannous (0.25g) effect
Hour, 60g epoxy resin E-51 is then added, being warming up to 95 DEG C, the reaction was continued 2.5 hours, obtains silicon-based polyurethane performed polymer and connects
The epoxy resin of branch；
2, the preparation of single sealing end polyethylene polyamine
It will be added in another four-hole bottle in 146g triethylene tetramine, control temperature at 70 DEG C, 130g butyl is slowly added dropwise
Glycidol ether, the reaction was continued 3 hours in 70 DEG C after being added dropwise, and obtains single sealing end polyethylene polyamine；
3, the preparation of functional epoxy resin curing agent
Single sealing end polyethylene polyamine prepared by 46g step 2 be placed in equipped with blender, reflux condensing tube, thermometer four
In mouth flask, the silicon-based polyurethane performed polymer Graft Epoxy Resin of 72g step 1 preparation of propylene glycol monomethyl ether dissolution is slowly added dropwise,
It is reacted 4 hours at 80 DEG C, is cooled to 60 DEG C, 12.5g glacial acetic acid is added into salt, the reaction was continued at 60 DEG C 0.5 hour, reaction
After vacuum distillation remove solvent, deionized water 100g is added, stirs 0.5 hour, is made aqueous epoxy resin curing agent, half
Clear, yellowish, solid content 54.3%, amine value 156.5KOH/g, viscosity 2400mPa.s.
Aqueous epoxy resin curing agent obtained and E-51 are mixed to get waterborne epoxy coatings in proportion, configuration proportion is such as
Under:
Component A: 38 grams of E-51
B component: 100 grams of 1 gained aqueous epoxy resin curing agent of embodiment
Two components are uniformly mixed up to waterborne epoxy coatings, performance detection is as follows:
| Detection project | Testing result |
| Surface drying time/min | 100 |
| Do solid work the time/h | <24 |
| Pencil hardness | 2H |
| Adhesive force/grade | 1 |
| Flexibility/mm | 1 |
| Impact resistance/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 310 |
| Water resistance (56h) | It is unchanged |
| Oil resistivity (machine oil, 30d) | It is unchanged |
Embodiment 2:
In the present embodiment functional epoxy resin curing agent the preparation method is as follows:
1, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
25g polyethers N220 is added in dry four-hole boiling flask, dehydration 2.0 hours is vacuumized at 120 DEG C, is then cooled down
To 50 DEG C, 10.5g hydroxy silicon oil and 11.1g IPDI is added, reacts 2 in 80 DEG C under octoate catalyst stannous (0.15g) effect
Hour, 40g epoxy resin E-51 is then added, being warming up to 90 DEG C, the reaction was continued 2.5 hours, obtains silicon-based polyurethane performed polymer and connects
The epoxy resin of branch；
2, the preparation of single sealing end polyethylene polyamine
It will be added in another four-hole bottle in 146g triethylene tetramine, control temperature at 70 DEG C, 130g butyl is slowly added dropwise
Glycidol ether, the reaction was continued 3 hours in 70 DEG C after being added dropwise, and obtains single sealing end polyethylene polyamine；
3, the preparation of functional epoxy resin curing agent
Single sealing end polyethylene polyamine prepared by 50g step 2 be placed in equipped with blender, reflux condensing tube, thermometer four
In mouth flask, the silicon-based polyurethane performed polymer grafted epoxy tree of 68.4g step 1 preparation of propylene glycol monomethyl ether dissolution is slowly added dropwise
Rouge reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, and 10.9g glacial acetic acid is added into salt, and the reaction was continued at 60 DEG C 0.5 hour,
Vacuum distillation removes solvent after reaction, and deionized water 110g is added, and stirs 0.5 hour, and aqueous epoxy resins solidification is made
Agent, translucent light yellow, solid content 50.8%, amine value 159.9KOH/g, viscosity 2500mPa.s.
Aqueous epoxy resin curing agent obtained and E-51 are mixed to get waterborne epoxy coatings in proportion, configuration proportion is such as
Under:
Component A: 42.5 grams of E-51
B component: 100 grams of 2 gained aqueous epoxy resin curing agent of embodiment
Two components are uniformly mixed up to waterborne epoxy coatings, performance detection is as follows:
| Detection project | Testing result |
| Surface drying time/min | 120 |
| Do solid work the time/h | <24 |
| Pencil hardness | 2H |
| Adhesive force/grade | 1 |
| Flexibility/mm | 1 |
| Impact resistance/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 305 |
| Water resistance (56h) | It is unchanged |
| Oil resistivity (machine oil, 30d) | It is unchanged |
Embodiment 3:
In the present embodiment functional epoxy resin curing agent the preparation method is as follows:
1, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
30g polyethers N210 is added in dry four-hole boiling flask, dehydration 2.0 hours is vacuumized at 120 DEG C, is then cooled down
To 50 DEG C, 16.8g hydroxy silicon oil and 17.4g TDI is added, reacts 2 in 70 DEG C under octoate catalyst stannous (0.22g) effect
Hour, 60g epoxy resin E-51 is then added, being warming up to 85 DEG C, the reaction was continued 2.5 hours, obtains silicon-based polyurethane performed polymer and connects
The epoxy resin of branch；
2, the preparation of single sealing end polyethylene polyamine
It will be added in another four-hole bottle in 146g triethylene tetramine, control temperature at 70 DEG C, 130g butyl is slowly added dropwise
Glycidol ether, the reaction was continued 3 hours in 70 DEG C after being added dropwise, and obtains single sealing end polyethylene polyamine；
3, the preparation of functional epoxy resin curing agent
Single sealing end polyethylene polyamine prepared by 50g step 2 be placed in equipped with blender, reflux condensing tube, thermometer four
In mouth flask, the silicon-based polyurethane performed polymer Graft Epoxy Resin of 75g step 1 preparation of propylene glycol monomethyl ether dissolution is slowly added dropwise,
It is reacted 4 hours at 80 DEG C, is cooled to 60 DEG C, 10.9g glacial acetic acid is added into salt, the reaction was continued at 60 DEG C 0.5 hour, reaction
After vacuum distillation remove solvent, deionized water 110g is added, stirs 0.5 hour, is made aqueous epoxy resin curing agent, half
Clear, yellowish, solid content 52.1%, amine value 162KOH/g, viscosity 2300mP.s.
Aqueous epoxy resin curing agent obtained and E-51 are mixed to get waterborne epoxy coatings in proportion, configuration proportion is such as
Under:
Component A: 43 grams of E-51
B component: 100 grams of 3 gained aqueous epoxy resin curing agent of example
Two components are uniformly mixed up to waterborne epoxy coatings, performance detection is as follows:
| Detection project | Testing result |
| Surface drying time/min | 100 |
| Do solid work the time/h | <24 |
| Pencil hardness | 3H |
| Adhesive force/grade | 1 |
| Flexibility/mm | 1 |
| Impact resistance/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 318 |
| Water resistance (56h) | It is unchanged |
| Oil resistivity (machine oil, 30d) | It is unchanged |
Embodiment 4:
In the present embodiment functional epoxy resin curing agent the preparation method is as follows:
1, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
20g polyethers N220 is added in dry four-hole boiling flask, dehydration 2.0 hours is vacuumized at 120 DEG C, is then cooled down
To 50 DEG C, 12.6g hydroxy silicon oil and 17.4g TDI is added, reacts 2 in 70 DEG C under octoate catalyst stannous (0.15g) effect
Hour, 40g epoxy resin E-51 is then added, being warming up to 85 DEG C, the reaction was continued 2.5 hours, obtains silicon-based polyurethane performed polymer and connects
The epoxy resin of branch；
2, the preparation of single sealing end polyethylene polyamine
It will be added in another four-hole bottle in 146g triethylene tetramine, control temperature at 70 DEG C, 130g butyl is slowly added dropwise
Glycidol ether, the reaction was continued 3 hours in 70 DEG C after being added dropwise, and obtains single sealing end polyethylene polyamine；
3, the preparation of functional epoxy resin curing agent
Single sealing end polyethylene polyamine prepared by 50g step 2 be placed in equipped with blender, reflux condensing tube, thermometer four
In mouth flask, the silicon-based polyurethane performed polymer grafted epoxy tree of 81.5g step 1 preparation of propylene glycol monomethyl ether dissolution is slowly added dropwise
Rouge reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, and 10.9g glacial acetic acid is added into salt, and the reaction was continued at 60 DEG C 0.5 hour,
Vacuum distillation removes solvent after reaction, and deionized water 120g is added, and stirs 0.5 hour, and aqueous epoxy resins solidification is made
Agent, translucent light yellow, solid content 51.3%, amine value 146.2KOH/g, viscosity 2500mPa.s.
Aqueous epoxy resin curing agent obtained and E-51 are mixed to get waterborne epoxy coatings in proportion, configuration proportion is such as
Under:
Component A: 52 grams of E-51
B component: 100 grams of 4 gained aqueous epoxy resin curing agent of example
Two components are uniformly mixed up to waterborne epoxy coatings, performance detection is as follows:
| Detection project | Testing result |
| Surface drying time/min | 110 |
| Do solid work the time/h | <24 |
| Pencil hardness | 2H |
| Adhesive force/grade | 1 |
| Flexibility/mm | 1 |
| Impact resistance/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 314 |
| Water resistance (56h) | It is unchanged |
| Oil resistivity (machine oil, 30d) | It is unchanged |
Embodiment 5:
In the present embodiment functional epoxy resin curing agent the preparation method is as follows:
1, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
35g polyethers N210 is added in dry four-hole boiling flask, dehydration 2.0 hours is vacuumized at 120 DEG C, is then cooled down
To 50 DEG C, 12.6g hydroxy silicon oil and 22.2g IPDI is added, reacts 2 in 90 DEG C under octoate catalyst stannous (0.22g) effect
Hour, 60g epoxy resin E-51 is then added, being warming up to 95 DEG C, the reaction was continued 2.5 hours, obtains silicon-based polyurethane performed polymer and connects
The epoxy resin of branch；
2, the preparation of single sealing end polyethylene polyamine
It will be added in another four-hole bottle in 94.5g tetraethylenepentamine, control temperature at 70 DEG C, 65g butyl is slowly added dropwise
Glycidol ether, the reaction was continued 3 hours in 70 DEG C after being added dropwise, and obtains single sealing end polyethylene polyamine；
3, the preparation of functional epoxy resin curing agent
Single sealing end polyethylene polyamine prepared by 40g step 2 be placed in equipped with blender, reflux condensing tube, thermometer four
In mouth flask, the silicon-based polyurethane performed polymer grafted epoxy tree of 54.3g step 1 preparation of propylene glycol monomethyl ether dissolution is slowly added dropwise
Rouge reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, and 9.4g glacial acetic acid is added into salt, the reaction was continued at 60 DEG C 0.5 hour, instead
Vacuum distillation removes solvent after answering, and deionized water 100g is added, and stirs 0.5 hour, and aqueous epoxy resin curing agent is made,
It is translucent light yellow, solid content 47.6%, amine value 161.5KOH/g, viscosity 2400mPa.s.
Aqueous epoxy resin curing agent obtained and E-51 are mixed to get waterborne epoxy coatings in proportion, configuration proportion is such as
Under:
Component A: 56 grams of E-51
B component: 100 grams of 5 gained aqueous epoxy resin curing agent of example
Two components are uniformly mixed up to waterborne epoxy coatings, performance detection is as follows:
| Detection project | Testing result |
| Surface drying time/min | 100 |
| Do solid work the time/h | <24 |
| Pencil hardness | 3H |
| Adhesive force/grade | 1 |
| Flexibility/mm | 1 |
| Impact resistance/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 320 |
| Water resistance (56h) | It is unchanged |
| Oil resistivity (machine oil, 30d) | It is unchanged |
Claims (9)
1. a kind of preparation method of functional epoxy resin curing agent, it is characterised in that include the following steps:
(1) preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
Polyether Glycols heating is vacuumized, is dehydrated 2.0 hours in 120 DEG C, is then cooled to 50 DEG C, hydroxy silicon oil and two is added
Isocyanates, control-NCO and-OH molar ratio are 2.0-3.0:1.0, under the action of catalyst in 50-90 DEG C of reaction 1.5-2.5
Hour, epoxy resin E-51 is then added, being warming up to 70-95 DEG C, the reaction was continued 2-3 hours, obtains silicon-based polyurethane performed polymer and connects
The epoxy resin of branch；
(2) preparation of single sealing end polyethylene polyamine
Single glycidyl oxirane is slowly added dropwise into polyethylene polyamine, single glycidyl oxirane and polyethylene polyamine rub
You react 3-4 hours at 60-80 DEG C than being 1:1, obtain single sealing end polyethylene polyamine；
(3) preparation of functional epoxy resin curing agent
Epoxy resin and solvent that silicon-based polyurethane performed polymer is grafted are added dropwise in single sealing end polyethylene polyamine, wherein control ring
Oxygroup and the molar ratio of single sealing end polyethylene polyamine are 1:1-1.5, react 3-4 hours at 60-80 DEG C, organic acid is then added
At salt, the molar ratio of organic acid and remaining amine hydrogen is 1:4-5, the reaction was continued at 55-65 DEG C 0.5-1 hours, after reaction
Vacuum distillation removes solvent, and deionized water is added, and aqueous epoxy resin curing agent is made, and solid content is controlled in 45-55%.
2. preparation method according to claim 1, it is characterised in that:
The number-average molecular weight of the polyether Glycols is 400-4000.
3. preparation method according to claim 1, it is characterised in that:
The diisocyanate is toluene di-isocyanate(TDI), isophorone diisocyanate, hexamethylene diisocyanate or two
Methylenebis phenyl isocyanate.
4. preparation method according to claim 1, it is characterised in that:
The catalyst is dibutyl tin dilaurate or stannous octoate, and additive amount is polyether Glycols, diisocyanate and ring
The 0.2-0.4% of oxygen resin E-51 gross mass.
5. preparation method according to claim 1, it is characterised in that:
The additive amount of the epoxy resin E-51 is the 45- of polyether Glycols, diisocyanate and epoxy resin E-51 gross mass
60%.
6. preparation method according to claim 1, it is characterised in that:
The list glycidyl oxirane is butyl glycidyl ether, phenyl glycidyl ether, C12-14Appointing in glycidol ether
Meaning is one or more of.
7. preparation method according to claim 1, it is characterised in that:
The polyethylene polyamine is m-phenylene diamine (MPD), diethylenetriamine, triethylene tetramine or tetraethylenepentamine.
8. preparation method according to claim 1, it is characterised in that:
The organic acid is acetic acid or oxalic acid.
9. preparation method according to claim 1, it is characterised in that:
The solvent is one or more of propylene glycol monomethyl ether, propylene-glycol ethyl ether, ethylene glycol ethyl ether.
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| CN107840940B (en) * | 2017-10-25 | 2020-02-07 | 中南林业科技大学 | Preparation method of curing agent for epoxy powder coating |
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| CN112062968B (en) * | 2020-09-01 | 2022-05-24 | 深圳市聚芯源新材料技术有限公司 | Epoxy resin curing agent and separator for manufacturing same |
| CN113461960B (en) * | 2021-07-02 | 2022-06-10 | 安徽大学 | Preparation method of hyperbranched waterborne epoxy resin curing agent |
| CN114395101A (en) * | 2022-01-22 | 2022-04-26 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method and application of epoxy resin toughening agent |
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| CN115572528B (en) * | 2022-11-15 | 2023-06-20 | 佛山市高明区首邦化工有限公司 | Anticorrosive paint for furniture and preparation method and application thereof |
| CN116284655B (en) * | 2023-01-10 | 2024-01-09 | 中威北化科技有限公司 | Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin |
| CN116284800A (en) * | 2023-05-18 | 2023-06-23 | 广州恒峰新材料科技有限公司 | Water-based epoxy resin curing agent and preparation method of water-based epoxy paint |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583816A (en) * | 2003-08-21 | 2005-02-23 | 中国科学院化学研究所 | Silicon containing organic amine epoxy resin curing agent |
| CN1752163A (en) * | 2005-10-20 | 2006-03-29 | 同济大学 | A kind of aqueous epoxide resin paint and preparation method thereof |
| CN101696263A (en) * | 2009-10-29 | 2010-04-21 | 复旦大学 | Epoxy resin curing agent, method for preparing same and application thereof |
| CN101824133A (en) * | 2010-04-28 | 2010-09-08 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
| CN102268126A (en) * | 2011-06-01 | 2011-12-07 | 上海大学 | Preparation method of organosilicon latent epoxy resin curing agent |
| CN102675596A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Organic silicon epoxy resin curing agent and epoxy curing system containing same |
| CN103145955A (en) * | 2013-02-04 | 2013-06-12 | 广东工业大学 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
| CN103923320A (en) * | 2014-04-02 | 2014-07-16 | 浙江大学 | Branched organosilicon epoxy resin curing agent and epoxy curing system |
| CN105315436A (en) * | 2015-10-23 | 2016-02-10 | 蓝星（成都）新材料有限公司 | Polyether type epoxy resin curing agent and preparation method thereof |
-
2016
- 2016-09-13 CN CN201610821180.9A patent/CN106397780B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583816A (en) * | 2003-08-21 | 2005-02-23 | 中国科学院化学研究所 | Silicon containing organic amine epoxy resin curing agent |
| CN1752163A (en) * | 2005-10-20 | 2006-03-29 | 同济大学 | A kind of aqueous epoxide resin paint and preparation method thereof |
| CN101696263A (en) * | 2009-10-29 | 2010-04-21 | 复旦大学 | Epoxy resin curing agent, method for preparing same and application thereof |
| CN101824133A (en) * | 2010-04-28 | 2010-09-08 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
| CN102268126A (en) * | 2011-06-01 | 2011-12-07 | 上海大学 | Preparation method of organosilicon latent epoxy resin curing agent |
| CN102675596A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Organic silicon epoxy resin curing agent and epoxy curing system containing same |
| CN103145955A (en) * | 2013-02-04 | 2013-06-12 | 广东工业大学 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
| CN103923320A (en) * | 2014-04-02 | 2014-07-16 | 浙江大学 | Branched organosilicon epoxy resin curing agent and epoxy curing system |
| CN105315436A (en) * | 2015-10-23 | 2016-02-10 | 蓝星（成都）新材料有限公司 | Polyether type epoxy resin curing agent and preparation method thereof |
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