CN106397780A - Preparation method of functional epoxy resin curing agent - Google Patents
Preparation method of functional epoxy resin curing agent Download PDFInfo
- Publication number
- CN106397780A CN106397780A CN201610821180.9A CN201610821180A CN106397780A CN 106397780 A CN106397780 A CN 106397780A CN 201610821180 A CN201610821180 A CN 201610821180A CN 106397780 A CN106397780 A CN 106397780A
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- CN
- China
- Prior art keywords
- epoxy resin
- preparation
- polyethylene polyamine
- curing agent
- silicon
- Prior art date
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- Granted
Links
- 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
- 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 26
- 239000004814 polyurethane Substances 0.000 claims description 25
- 229920002635 polyurethane Polymers 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 23
- 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
- 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
- 239000002904 solvent Substances 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
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 7
- 230000000903 blocking effect Effects 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 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
- 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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 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
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 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
- 150000002118 epoxides Chemical class 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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 7
- 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
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012467 final product Substances 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
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- 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
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product 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
First, technical field
The present invention relates to a kind of preparation method of firming agent, specifically a kind of system of functional epoxy resin curing agent
Preparation Method, belongs to firming agent technical field.
2nd, background technology
Epoxy resin is widely used in the fields such as building, chemical industry, traffic, electronics, product mainly based on solvent-borne type, in a large number
Organic solvent using meeting, environment is caused with very big harm.Though having good cementability, insulating properties and excellent antiseptic property,
But there is also the shortcomings of toughness and poor impact resistance so as to application is subject to a definite limitation.Therefore, to epoxy resin roughening and aqueouss
The research changed has great importance.
Introduce in firming agent that soft segment is epoxy resin toughened has a clear superiority than additional toughener.Polyurethane has light
The advantages of good, the elastic height of damp degree, bonding force are strong, can be combined with epoxy resin in many ways, be modified toughened epoxy resin
Effective ways.But polyurethane toughened epoxy resin can cause the reduction of system thermostability, and organosilicon has the chemistry knot of uniqueness
Structure, its surface energy is relatively low, can give polymer-modified film excellent water-fast, resistance to surface enrichment in film forming procedure
The performances such as time, resistance to greasy dirt and high-low temperature resistant.Organosilicon and polyurethane structural it have been simultaneously introduced in firming agent, itself and epoxy resin
The prepared toughness of epoxy resin cure film of solidification, thermostability resistance to water are all improved.
3rd, content of the invention
The present invention is intended to provide a kind of preparation method of functional epoxy resin curing agent, firming agent of the present invention can be simultaneously newborn
Change and cured epoxy resin, and toughness, thermostability and the resistance to water of epoxy resin can be improved.
The preparation method of functional epoxy resin curing agent of the present invention, comprises the steps：
(1) preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
Polyether Glycols are heated evacuation, is dehydrated 2.0 hours in 120 DEG C, is subsequently cooled to 50 DEG C, add hydroxy silicon oil
And diisocyanate, control-NCO and-OH mol ratio to be 2.0-3.0:1.0, the mole of hydroxyl is with polyether Glycols and hydroxyl
Total hydroxyl meter of silicone oil, hydroxy silicon oil is 1 with the mass ratio of polyether Glycols:1.5-3, in 50-90 DEG C under catalyst action
Reaction 1.5-2.5 hour, is subsequently added epoxy resin E-51, is warming up to 70-95 DEG C and continues reaction 2-3 hour, obtains siliceous poly-
The epoxy resin of urethane performed polymer grafting；
The number-average molecular weight of described polyether Glycols is 400-4000.
Described diisocyanate is toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate (IPDI), hexa-methylene
Diisocyanate (HDI) or methyl diphenylene diisocyanate (MDI).
Described hydroxy silicon oil is small-molecular-weight hydroxy silicon oil, molecular weight 800-900.
Described catalyst is dibutyl tin laurate or stannous octoate, and addition is polyether Glycols, diisocyanate
0.2-0.4% with epoxy resin E-51 gross mass.
The addition of described epoxy resin E-51 is polyether Glycols, diisocyanate and epoxy resin E-51 gross mass
45-60%.
(2) single preparation blocking polyethylene polyamine
Single glycidyl oxirane is slowly added dropwise to polyethylene polyamine, single glycidyl oxirane and polyethylene polyamine
Mol ratio be 1:1, react 3-4 hour at 60-80 DEG C, obtain single end-blocking polyethylene polyamine；
Described single glycidyl oxirane is butyl glycidyl ether, phenyl glycidyl ether, C12-14In glycidyl ether
Any one or a few.
Described polyethylene polyamine is m-diaminobenzene., diethylenetriamine, triethylene tetramine or TEPA.
(3) preparation of functional epoxy resin curing agent
The epoxy resin of silicon-based polyurethane performed polymer grafting and solvent are dropped in single end-blocking polyethylene polyamine, wherein controls
Epoxy radicals processed are 1 with the mol ratio of single end-blocking polyethylene polyamine：1-1.5, reacts 3-4 hour at 60-80 DEG C, has been subsequently added
Machine acid becomes salt, and organic acid is 1 with the mol ratio of remaining amine hydrogen：4-5, continues reaction 0.5-1 hour, reaction knot at 55-65 DEG C
After bundle, vacuum distillation removes solvent, adds deionized water, prepared aqueous epoxy resin curing agent, solid content controls in 45-55%.
Described organic acid is acetic acid or oxalic acid.
Described solvent is one or more of propylene glycol monomethyl ether, propylene-glycol ethyl ether, ethylene glycol.
Compared with prior art, the present invention has advantages below：
1st, firming agent of the present invention has good emulsification to liquid epoxies, and is curable epoxy tree under room temperature
Fat.
2nd, the present invention prepares the poly- ammonia of siliceous terminal isocyanate group with polyether Glycols, diisocyanate and hydroxy silicon oil first
Ester performed polymer, then Graft Epoxy Resin prepare the epoxy resin of silicon-based polyurethane performed polymer grafting, the preparation heat-resisting water of toughness
Property epoxy curing agent, has been simultaneously introduced polyurethane and organosilicon structures, can either improve the toughness of cured film, and can improve
The thermostability of cured film and resistance to water.
4th, specific embodiment
Embodiment 1：
In the present embodiment, the preparation method of functional epoxy resin curing agent is as follows：
1st, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
35g polyethers N210 is added in dry four-hole boiling flask, evacuation is dehydrated 2.0 hours at 120 DEG C, subsequently lower the temperature
To 50 DEG C, add 12.6g hydroxy silicon oil and 22.2g IPDI, under octoate catalyst stannous (0.25g) effect, react 2 in 90 DEG C
Hour, it is subsequently added 60g epoxy resin E-51, is warming up to 95 DEG C and continues reaction 2.5 hours, obtain silicon-based polyurethane performed polymer and connect
The epoxy resin of branch；
2nd, single preparation blocking polyethylene polyamine
To be added in 146g triethylene tetramine in another four-hole bottle, control temperature at 70 DEG C, be slowly added dropwise 130g butyl
Glycidyl ether, completion of dropping continues reaction 3 hours after 70 DEG C, obtains single end-blocking polyethylene polyamine；
3rd, the preparation of functional epoxy resin curing agent
List prepared by 46g step 2 block polyethylene polyamine be placed in equipped with agitator, reflux condensing tube, thermometer four
In mouth flask, it is slowly added dropwise the silicon-based polyurethane performed polymer Graft Epoxy Resin of 72g step 1 preparation of propylene glycol monomethyl ether dissolving,
React 4 hours at 80 DEG C, be cooled to 60 DEG C, add 12.5g glacial acetic acid to become salt, continue reaction 0.5 hour, reaction at 60 DEG C
After end, vacuum distillation removes solvent, adds deionized water 100g, stirs 0.5 hour, prepared aqueous epoxy resin curing agent, and half
Clear, yellowish, solid content is 54.3%, and amine number is 156.5KOH/g, and viscosity is 2400mPa.s.
The aqueous epoxy resin curing agent being obtained is mixed in proportion with E-51 and obtains aqueous epoxy coating, configuration proportion is such as
Under：
Component A：38 grams of E-51
B component：100 grams of embodiment 1 gained aqueous epoxy resin curing agent
Two component mix homogeneously are obtained final product aqueous epoxy coating, 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/level | 1 |
| Pliability/mm | 1 |
| Resistance to impact/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 310 |
| Resistance to water (56h) | Unchanged |
| Oil resistivity (machine oil, 30d) | Unchanged |
Embodiment 2：
In the present embodiment, the preparation method of functional epoxy resin curing agent is as follows：
1st, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
25g polyethers N220 is added in dry four-hole boiling flask, evacuation is dehydrated 2.0 hours at 120 DEG C, subsequently lower the temperature
To 50 DEG C, add 10.5g hydroxy silicon oil and 11.1g IPDI, under octoate catalyst stannous (0.15g) effect, react 2 in 80 DEG C
Hour, it is subsequently added 40g epoxy resin E-51, is warming up to 90 DEG C and continues reaction 2.5 hours, obtain silicon-based polyurethane performed polymer and connect
The epoxy resin of branch；
2nd, single preparation blocking polyethylene polyamine
To be added in 146g triethylene tetramine in another four-hole bottle, control temperature at 70 DEG C, be slowly added dropwise 130g butyl
Glycidyl ether, completion of dropping continues reaction 3 hours after 70 DEG C, obtains single end-blocking polyethylene polyamine；
3rd, the preparation of functional epoxy resin curing agent
List prepared by 50g step 2 block polyethylene polyamine be placed in equipped with agitator, reflux condensing tube, thermometer four
In mouth flask, it is slowly added dropwise the silicon-based polyurethane performed polymer grafted epoxy tree of 68.4g step 1 preparation of propylene glycol monomethyl ether dissolving
Fat, reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, adds 10.9g glacial acetic acid to become salt, continues reaction 0.5 hour at 60 DEG C,
Reaction terminates rear vacuum distillation and removes solvent, adds deionized water 110g, stirs 0.5 hour, prepared aqueous epoxy resins solidification
Agent, translucent light yellow, solid content is 50.8%, and amine number is 159.9KOH/g, and viscosity is 2500mPa.s.
The aqueous epoxy resin curing agent being obtained is mixed in proportion with E-51 and obtains aqueous epoxy coating, configuration proportion is such as
Under：
Component A：42.5 grams of E-51
B component：100 grams of embodiment 2 gained aqueous epoxy resin curing agent
Two component mix homogeneously are obtained final product aqueous epoxy coating, 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/level | 1 |
| Pliability/mm | 1 |
| Resistance to impact/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 305 |
| Resistance to water (56h) | Unchanged |
| Oil resistivity (machine oil, 30d) | Unchanged |
Embodiment 3：
In the present embodiment, the preparation method of functional epoxy resin curing agent is as follows：
1st, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
30g polyethers N210 is added in dry four-hole boiling flask, evacuation is dehydrated 2.0 hours at 120 DEG C, subsequently lower the temperature
To 50 DEG C, add 16.8g hydroxy silicon oil and 17.4g TDI, under octoate catalyst stannous (0.22g) effect, react 2 in 70 DEG C
Hour, it is subsequently added 60g epoxy resin E-51, is warming up to 85 DEG C and continues reaction 2.5 hours, obtain silicon-based polyurethane performed polymer and connect
The epoxy resin of branch；
2nd, single preparation blocking polyethylene polyamine
To be added in 146g triethylene tetramine in another four-hole bottle, control temperature at 70 DEG C, be slowly added dropwise 130g butyl
Glycidyl ether, completion of dropping continues reaction 3 hours after 70 DEG C, obtains single end-blocking polyethylene polyamine；
3rd, the preparation of functional epoxy resin curing agent
List prepared by 50g step 2 block polyethylene polyamine be placed in equipped with agitator, reflux condensing tube, thermometer four
In mouth flask, it is slowly added dropwise the silicon-based polyurethane performed polymer Graft Epoxy Resin of 75g step 1 preparation of propylene glycol monomethyl ether dissolving,
React 4 hours at 80 DEG C, be cooled to 60 DEG C, add 10.9g glacial acetic acid to become salt, continue reaction 0.5 hour, reaction at 60 DEG C
After end, vacuum distillation removes solvent, adds deionized water 110g, stirs 0.5 hour, prepared aqueous epoxy resin curing agent, and half
Clear, yellowish, solid content is 52.1%, and amine number is 162KOH/g, and viscosity is 2300mP.s.
The aqueous epoxy resin curing agent being obtained is mixed in proportion with E-51 and obtains aqueous epoxy coating, configuration proportion is such as
Under：
Component A：43 grams of E-51
B component：100 grams of example 3 gained aqueous epoxy resin curing agent
Two component mix homogeneously are obtained final product aqueous epoxy coating, 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/level | 1 |
| Pliability/mm | 1 |
| Resistance to impact/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 318 |
| Resistance to water (56h) | Unchanged |
| Oil resistivity (machine oil, 30d) | Unchanged |
Embodiment 4：
In the present embodiment, the preparation method of functional epoxy resin curing agent is as follows：
1st, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
20g polyethers N220 is added in dry four-hole boiling flask, evacuation is dehydrated 2.0 hours at 120 DEG C, subsequently lower the temperature
To 50 DEG C, add 12.6g hydroxy silicon oil and 17.4g TDI, under octoate catalyst stannous (0.15g) effect, react 2 in 70 DEG C
Hour, it is subsequently added 40g epoxy resin E-51, is warming up to 85 DEG C and continues reaction 2.5 hours, obtain silicon-based polyurethane performed polymer and connect
The epoxy resin of branch；
2nd, single preparation blocking polyethylene polyamine
To be added in 146g triethylene tetramine in another four-hole bottle, control temperature at 70 DEG C, be slowly added dropwise 130g butyl
Glycidyl ether, completion of dropping continues reaction 3 hours after 70 DEG C, obtains single end-blocking polyethylene polyamine；
3rd, the preparation of functional epoxy resin curing agent
List prepared by 50g step 2 block polyethylene polyamine be placed in equipped with agitator, reflux condensing tube, thermometer four
In mouth flask, it is slowly added dropwise the silicon-based polyurethane performed polymer grafted epoxy tree of 81.5g step 1 preparation of propylene glycol monomethyl ether dissolving
Fat, reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, adds 10.9g glacial acetic acid to become salt, continues reaction 0.5 hour at 60 DEG C,
Reaction terminates rear vacuum distillation and removes solvent, adds deionized water 120g, stirs 0.5 hour, prepared aqueous epoxy resins solidification
Agent, translucent light yellow, solid content is 51.3%, and amine number is 146.2KOH/g, and viscosity is 2500mPa.s.
The aqueous epoxy resin curing agent being obtained is mixed in proportion with E-51 and obtains aqueous epoxy coating, configuration proportion is such as
Under：
Component A：52 grams of E-51
B component：100 grams of example 4 gained aqueous epoxy resin curing agent
Two component mix homogeneously are obtained final product aqueous epoxy coating, 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/level | 1 |
| Pliability/mm | 1 |
| Resistance to impact/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 314 |
| Resistance to water (56h) | Unchanged |
| Oil resistivity (machine oil, 30d) | Unchanged |
Embodiment 5：
In the present embodiment, the preparation method of functional epoxy resin curing agent is as follows：
1st, the preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
35g polyethers N210 is added in dry four-hole boiling flask, evacuation is dehydrated 2.0 hours at 120 DEG C, subsequently lower the temperature
To 50 DEG C, add 12.6g hydroxy silicon oil and 22.2g IPDI, under octoate catalyst stannous (0.22g) effect, react 2 in 90 DEG C
Hour, it is subsequently added 60g epoxy resin E-51, is warming up to 95 DEG C and continues reaction 2.5 hours, obtain silicon-based polyurethane performed polymer and connect
The epoxy resin of branch；
2nd, single preparation blocking polyethylene polyamine
To be added in 94.5g TEPA in another four-hole bottle, control temperature at 70 DEG C, be slowly added dropwise 65g butyl
Glycidyl ether, completion of dropping continues reaction 3 hours after 70 DEG C, obtains single end-blocking polyethylene polyamine；
3rd, the preparation of functional epoxy resin curing agent
List prepared by 40g step 2 block polyethylene polyamine be placed in equipped with agitator, reflux condensing tube, thermometer four
In mouth flask, it is slowly added dropwise the silicon-based polyurethane performed polymer grafted epoxy tree of 54.3g step 1 preparation of propylene glycol monomethyl ether dissolving
Fat, reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, adds 9.4g glacial acetic acid to become salt, continues reaction 0.5 hour, instead at 60 DEG C
After should terminating, vacuum distillation removes solvent, adds deionized water 100g, stirs 0.5 hour, prepared aqueous epoxy resin curing agent,
Translucent light yellow, solid content is 47.6%, and amine number is 161.5KOH/g, and viscosity is 2400mPa.s.
The aqueous epoxy resin curing agent being obtained is mixed in proportion with E-51 and obtains aqueous epoxy coating, configuration proportion is such as
Under：
Component A：56 grams of E-51
B component：100 grams of example 5 gained aqueous epoxy resin curing agent
Two component mix homogeneously are obtained final product aqueous epoxy coating, 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/level | 1 |
| Pliability/mm | 1 |
| Resistance to impact/Kg.cm | ≥50 |
| Initial decomposition temperature/DEG C | 320 |
| Resistance to water (56h) | Unchanged |
| Oil resistivity (machine oil, 30d) | Unchanged |
Claims (9)
1. a kind of preparation method of functional epoxy resin curing agent is it is characterised in that comprise the steps：
(1) preparation of the epoxy resin of silicon-based polyurethane performed polymer grafting
Polyether Glycols are heated evacuation, is dehydrated 2.0 hours in 120 DEG C, is subsequently cooled to 50 DEG C, add hydroxy silicon oil and two
Isocyanates, control-NCO and-OH mol ratio to be 2.0-3.0:1.0, react 1.5-2.5 in 50-90 DEG C under catalyst action
Hour, it is subsequently added epoxy resin E-51, be warming up to 70-95 DEG C and continue reaction 2-3 hour, obtain silicon-based polyurethane performed polymer and connect
The epoxy resin of branch；
(2) single preparation blocking polyethylene polyamine
Single glycidyl oxirane is slowly added dropwise to polyethylene polyamine, single glycidyl oxirane is rubbed with polyethylene polyamine
That ratio is 1:1, react 3-4 hour at 60-80 DEG C, obtain single end-blocking polyethylene polyamine；
(3) preparation of functional epoxy resin curing agent
The epoxy resin of silicon-based polyurethane performed polymer grafting and solvent are dropped in single end-blocking polyethylene polyamine, wherein control ring
Epoxide is 1 with the mol ratio of single end-blocking polyethylene polyamine：1-1.5, reacts 3-4 hour at 60-80 DEG C, is subsequently added organic acid
Become salt, organic acid is 1 with the mol ratio of remaining amine hydrogen：4-5, continues reaction 0.5-1 hour, after reaction terminates at 55-65 DEG C
Vacuum distillation removes solvent, adds deionized water, prepared aqueous epoxy resin curing agent, solid content controls in 45-55%.
2. preparation method according to claim 1 it is characterised in that：
The number-average molecular weight of described polyether Glycols is 400-4000.
3. preparation method according to claim 1 it is characterised in that：
Described 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：
Described catalyst is dibutyl tin laurate or stannous octoate, and addition is polyether Glycols, diisocyanate and ring
The 0.2-0.4% of oxygen tree fat E-51 gross mass.
5. preparation method according to claim 1 it is characterised in that：
The addition of described 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：
Described single glycidyl oxirane is butyl glycidyl ether, phenyl glycidyl ether, C12-14Appointing in glycidyl ether
Anticipate one or more.
7. preparation method according to claim 1 it is characterised in that：
Described polyethylene polyamine is m-diaminobenzene., diethylenetriamine, triethylene tetramine or TEPA.
8. preparation method according to claim 1 it is characterised in that：
Described organic acid is acetic acid or oxalic acid.
9. preparation method according to claim 1 it is characterised in that：
Described solvent is one or more of propylene glycol monomethyl ether, propylene-glycol ethyl ether, ethylene glycol.
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