CN106397780A - Preparation method of functional epoxy resin curing agent - Google Patents
Preparation method of functional epoxy resin curing agent Download PDFInfo
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- 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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- epoxy resin
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- polyethylene polyamine
- curing agent
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- 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
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- 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
Abstract
The invention discloses a preparation method of a functional epoxy resin curing agent. Firstly, diisocyanate, polyether glycol and hydroxyl silicone oil react, a silicon-containing isocyanate-group-terminated polyurethane prepolymer is prepared, then epoxy resin E-51 is added, the reaction is continued, and silicon-containing polyurethane prepolymer grafted epoxy resin is prepared; monoepoxy glycidyl ether is dropwise added to polyethylene polyamine, and mono-terminated polyethylene polyamine is prepared; finally, the silicon-containing polyurethane prepolymer grafted epoxy resin is dropwise added to mono-terminated polyethylene polyamine, and the tough and heat-resistant water-based epoxy resin curing agent is obtained through reaction. The prepared curing agent has moderate equivalent weight, can emulsify and cure low-molecular-weight epoxy resin and is non-toxic and harmless, and the toughness, heat resistance and water resistance of a curing film prepared after epoxy resin is cured are greatly improved.
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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| CN116284655A (en) * | 2023-01-10 | 2023-06-23 | 中威北化科技有限公司 | Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin |
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