CN107286324A - A kind of preparation method of modified aqueous epoxy resin curing agent - Google Patents
A kind of preparation method of modified aqueous epoxy resin curing agent Download PDFInfo
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- CN107286324A CN107286324A CN201710424395.1A CN201710424395A CN107286324A CN 107286324 A CN107286324 A CN 107286324A CN 201710424395 A CN201710424395 A CN 201710424395A CN 107286324 A CN107286324 A CN 107286324A
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- epoxy resin
- curing agent
- modified aqueous
- aqueous epoxy
- resin curing
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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
- 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
- C08G59/5006—Amines aliphatic
- C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of preparation method of modified aqueous epoxy resin curing agent, belong to curing agent technical field.The present invention uses sodium hydroxide solution activating and regenerating cellulose fibre first, it is bonded after being ground again with triethylene tetramine, and occurs addition reaction with ethylene glycol diglycidylether, then through Epoxy resin chain extension, finally blocked with phenyl glycidyl ether, modified aqueous epoxy resin curing agent is made.Modified aqueous epoxy resin curing agent obtained by the present invention has good mechanical property and durability, it is nontoxic, without volatile organic solvent, not pollution of ecological environment, and without organic acid, metallic article will not be corroded, alkali resistance is strong, occur when alkaline filler is used together without unstable phenomenon, while to the no skin irritation of user.
Description
Technical field
The invention discloses a kind of preparation method of modified aqueous epoxy resin curing agent, belong to curing agent technical field.
Background technology
Epoxy resin has excellent tack, radioresistance, heat endurance, resistance to acids and bases, insulating properties and mechanical strength
Deng and be widely used in the every field such as coating, adhesive and composite.But epoxy resin is a kind of amorphous sticky
Liquid, heating is in plasticity, and without obvious fusing point, heated softening is gradually melted and stickness, water insoluble, and itself will not be hardened,
Therefore it is almost without single use value, and the not cladding polymer of generation tridimensional network is only reacted with curing agent just to be had
Application value.The chemical substance of different properties is just gradually solidify to form after a certain amount of curing agent is added, therefore, it is necessary to add solid
Agent, compositing formula resin, and curing reaction is carried out under certain condition, the high polymer material of space network is generated,
Various excellent performances can be just shown, as the epoxy material with real use value.As people will to environmental protection
That asks is increasingly urgent and strict, and the Water-borne modification of epoxy coating turns into the main trend of its development, and prepares matching aqueous
Epoxy curing agent is particularly important.
The report on aqueous epoxy resins is increasingly shown in many in recent years, and most of water-base epoxies are all by the master in resin
Hydrophilic radical is introduced in body structure, but can so destroy PART EPOXY base, so that solidification effect is undesirable.So passing through
Self-emulsifying aqueous curing agent is prepared to realize that the Water-borne modification of epoxy resin has great importance.Traditional aqueous epoxy resins
Curing agent is generally the modified product of aliphatic polyamine, mainly uses the epoxy radicals on epoxy resin to be reacted with fatty amine, in parent
Hydrophobic epoxy resin long-chain is introduced in aqueous preferable fatty amine, but is due to fatty amine and common epoxy resin addition
Afterwards, its hydrophily declines, therefore in order to ensure that curing agent has good dispersion effect in water, conventional organic acid is neutralized into
Salt, that is, form ionic aqueous epoxy curing agent.Because the presence of organic acid can cause film performance to decline, and it is coated in metal
Flash rusting is also easy to produce on product, environment can also be polluted, in addition, ionic aqueous epoxy curing agent is more sensitive to pH, when
When alkaline color stuffing is used together, easily there is unstable phenomenon.Therefore, research and develop that a kind of film is excellent, rustless property is good and
Good environment-friendly type aqueous epoxy curing agent is particularly important with alkaline filler compound property.
The content of the invention
The technical problems to be solved by the invention：Cause to apply for the organic acid in ionic aqueous epoxy resin curing agent
Film properties decline, and are coated on metallic article and are also easy to produce flash rusting, environment is polluted, and when alkaline filler is used together,
There is provided a kind of preparation method of modified aqueous epoxy resin curing agent for the problem of easily unstable phenomenon occur.Asked for solution technology
Topic, it is of the invention to be using technical scheme as described below：
（1）Regenerated celulose fibre is immersed in 1~2h of stirring in sodium hydroxide solution, filtration washing after 20~24h is stood and does
It is dry, obtain activating and regenerating cellulose fibre；
（2）It will be well mixed after the grinding sieving of activating and regenerating cellulose fibre with triethylene tetramine, at 60~65 DEG C, second be added dropwise
Hexanediol diglycidyl ether and 3~5h of stirring reaction, then epoxy resin is added dropwise, and it is heated to 70~80 DEG C, keeping temperature reaction 3
~4h, then phenyl glycidyl ether is added dropwise, 1~2h of insulation reaction is cooled to after 50~60 DEG C, adds deionized water, then
20~30min of stirring in high-speed shearing emulsion machine is transferred to, modified aqueous epoxy resin curing agent is obtained.
Step（2）The triethylene tetramine, ethylene glycol diglycidylether, epoxy resin, phenyl glycidyl ether and go
The parts by volume of ionized water is 590~600 parts of triethylene tetramines, 150~160 parts of ethylene glycol diglycidylethers, 180~210 parts
Epoxy resin, 90~120 parts of phenyl glycidyl ethers, 100~200 parts of deionized waters.
Step（2）The activating and regenerating cellulose fibre consumption is the 0.5~0.8% of triethylene tetramine quality.
Step（2）The epoxy resin is one kind in bisphenol A type epoxy resin E-51, E-44 or E-20.
The method have the benefit that：
The present invention utilizes sodium hydroxide solution activating and regenerating cellulose fibre, then it is bonded with triethylene tetramine, and with second two
Addition reaction occurs for alcohol diglycidyl ether, then through Epoxy resin chain extension, is finally blocked with phenyl glycidyl ether, is made with parent
Water macromolecular chain is skeleton, not only hydrophilic but also oleophylic the amphipathic solidification of the comb shape macromolecular of a large amount of epoxy-polyamines short chains of link
Agent structure, polyamines backbone causes paint film to have good pliability, resistance to acids and bases performance, the modified water-soluble obtained by the present invention
Epoxy curing agent has good mechanical property and durability, nontoxic, without volatile organic solvent, does not pollute life
State environment, and without organic acid, metallic article will not be corroded, alkali resistance is strong, goes out when alkaline filler is used together without unstable phenomenon
It is existing, while to the no skin irritation of user.
Embodiment
Weigh 20~30g regenerated celulose fibres, add during 300~350mL mass fractions are 10% sodium hydroxide solution,
Stirred with 300~400r/min after 1~2h, stand 20~24h of activation, then filtering, filter residue is washed with deionized to washing
Liquid is in neutrality, then filter residue is placed in drying box, and 3~5h is dried at 50~60 DEG C, activating and regenerating cellulose fibre is obtained, weighs
3~5g activating and regenerating cellulose fibres, are fitted into mortar and grind, and cross 400 mesh sieves, then by itself and 595~600mL triethylene tetramines
It is fitted into four-hole boiling flask, and disperses 3~4h with 300W ultrasonic echographies, then under 60~65 DEG C of waters bath with thermostatic control, with 1~2mL/
155~160mL ethylene glycol diglycidylethers are added dropwise in min, and after after completion of dropping, keeping temperature is simultaneously stirred with 300~400r/min
3~5h of reaction is mixed, pre-reaction liquid is obtained, then in the case where 300~400r/min is persistently stirred, into pre-reaction liquid, with 1~2mL/min
185~210mL epoxy resin is added dropwise, after after completion of dropping, being heated to 70~80 DEG C, keeping temperature reacts 3~4h, obtains prepolymerization
Reaction solution, in the case where persistently being stirred with 400~500r/min, into prepolymerization liquid, 90~120mL is added dropwise with 1~2mL/min
Phenyl glycidyl ether, after after completion of dropping, 1~2h is reacted under 70~80 DEG C of waters bath with thermostatic control, is cooled to after 50~60 DEG C, then
Add 100~200mL deionized waters, then continue in high-speed shearing emulsion machine, with 1000~1200r/min stirring 20~
30min, is cooled to after room temperature and discharges, obtain modified aqueous epoxy resin curing agent.The epoxy resin is bisphenol A type epoxy resin
One kind in E-51, E-44 or E-20.
Example 1
20g regenerated celulose fibres are weighed, add 300mL mass fractions in 10% sodium hydroxide solution, to stir with 300r/min
After 1h, activation 20h is stood, then filtering, filter residue is washed with deionized and is placed in drying box in neutrality, then by filter residue to cleaning solution
In, 3h is dried at 50 DEG C, activating and regenerating cellulose fibre is obtained, weighs 3g activating and regenerating cellulose fibres, be fitted into mortar and grind
Mill, crosses 400 mesh sieves, then it is fitted into four-hole boiling flask with 595mL triethylene tetramines, and disperses 3h with 300W ultrasonic echographies,
Again under 60 DEG C of waters bath with thermostatic control, 155mL ethylene glycol diglycidylethers, after after completion of dropping, keeping temperature are added dropwise with 1mL/min
And with 300r/min stirring reaction 3h, pre-reaction liquid is obtained, then in the case where 300r/min is persistently stirred, into pre-reaction liquid, with 1mL/
185mL bisphenol A type epoxy resin E-51 are added dropwise in min, and after after completion of dropping, being heated to 70 DEG C, keeping temperature reaction 3h obtains pre-polymerization
Reaction solution is closed, in the case where persistently being stirred with 400r/min, into prepolymerization liquid, 90mL phenyl glycidyls are added dropwise with 1mL/min sweet
Oily ether, after after completion of dropping, 1h is reacted under 70 DEG C of waters bath with thermostatic control, is cooled to after 50 DEG C, 100mL deionized waters are added, with
After be transferred in high-speed shearing emulsion machine, with 1000r/min stir 20min, be cooled to after room temperature discharge, obtain modified waterborne epoxy tree
Fat curing agent.
By volume 1:1.5, by epoxy resin E-51 and modified aqueous epoxy resin curing agent made from example 1 in room temperature
Under the conditions of stir 10min, you can be made waterborne epoxy coatings.
Example 2
25g regenerated celulose fibres are weighed, add 325mL mass fractions in 10% sodium hydroxide solution, to stir with 350r/min
After 1h, activation 22h is stood, then filtering, filter residue is washed with deionized and is placed in drying box in neutrality, then by filter residue to cleaning solution
In, 4h is dried at 55 DEG C, activating and regenerating cellulose fibre is obtained, weighs 4g activating and regenerating cellulose fibres, be fitted into mortar and grind
Mill, crosses 400 mesh sieves, then it is fitted into four-hole boiling flask with 598mL triethylene tetramines, and disperses 3h with 300W ultrasonic echographies,
Again under 63 DEG C of waters bath with thermostatic control, 158mL ethylene glycol diglycidylethers, after after completion of dropping, keeping temperature are added dropwise with 1mL/min
And with 350r/min stirring reaction 4h, pre-reaction liquid is obtained, then in the case where 350r/min is persistently stirred, into pre-reaction liquid, with 1mL/
197mL bisphenol A type epoxy resin E-44 are added dropwise in min, and after after completion of dropping, being heated to 75 DEG C, keeping temperature reaction 3h obtains pre-polymerization
Reaction solution is closed, in the case where persistently being stirred with 450r/min, into prepolymerization liquid, 105mL phenyl glycidyls are added dropwise with 1mL/min sweet
Oily ether, after after completion of dropping, 1h is reacted under 75 DEG C of waters bath with thermostatic control, is cooled to after 55 DEG C, 150mL deionized waters are added, with
After be transferred in high-speed shearing emulsion machine, with 1100r/min stir 25min, be cooled to after room temperature discharge, obtain modified waterborne epoxy tree
Fat curing agent.
By volume 1:1.5, by epoxy resin E-51 and modified aqueous epoxy resin curing agent made from example 2 in room temperature
Under the conditions of stir 10min, you can be made waterborne epoxy coatings.
Example 3
30g regenerated celulose fibres are weighed, add 350mL mass fractions in 10% sodium hydroxide solution, to stir with 400r/min
After 2h, activation 24h is stood, then filtering, filter residue is washed with deionized and is placed in drying box in neutrality, then by filter residue to cleaning solution
In, 5h is dried at 60 DEG C, activating and regenerating cellulose fibre is obtained, weighs 5g activating and regenerating cellulose fibres, be fitted into mortar and grind
Mill, crosses 400 mesh sieves, then it is fitted into four-hole boiling flask with 600mL triethylene tetramines, and disperses 4h with 300W ultrasonic echographies,
Again under 65 DEG C of waters bath with thermostatic control, 160mL ethylene glycol diglycidylethers, after after completion of dropping, keeping temperature are added dropwise with 2mL/min
And with 400r/min stirring reaction 5h, pre-reaction liquid is obtained, then in the case where 400r/min is persistently stirred, into pre-reaction liquid, with 2mL/
210mL bisphenol A type epoxy resin E-20 are added dropwise in min, and after after completion of dropping, being heated to 80 DEG C, keeping temperature reaction 4h obtains pre-polymerization
Reaction solution is closed, in the case where persistently being stirred with 500r/min, into prepolymerization liquid, 120mL phenyl glycidyls are added dropwise with 2mL/min sweet
Oily ether, after after completion of dropping, 2h is reacted under 80 DEG C of waters bath with thermostatic control, is cooled to after 60 DEG C, 200mL deionized waters are added, with
After be transferred in high-speed shearing emulsion machine, with 1200r/min stir 30min, be cooled to after room temperature discharge, obtain modified waterborne epoxy tree
Fat curing agent.
By volume 1:1.5, by epoxy resin E-51 and modified aqueous epoxy resin curing agent made from example 3 in room temperature
Under the conditions of stir 10min, you can be made waterborne epoxy coatings.
Comparative example：By volume 1:1.5, by epoxy resin E-51 and commercially available aqueous epoxy resin curing agent in room temperature condition
Lower stirring 10min, you can waterborne epoxy coatings is made.
To the waterborne epoxy coatings prepared using the gained modified aqueous epoxy resin curing agent of example 1~3 and using commercially available
The waterborne epoxy coatings that aqueous epoxy resin curing agent is prepared carries out performance detection, its testing result such as table 1 below：
Table 1
In summary, modified water-soluble oxygen resin curing agent produced by the present invention has preferable filming performance, with epoxy resin master
Agent is used in mixed way, the levelability of energy reinforced epoxy coating, while preferable rustless property can be played in metallic substrate surface,
And the epoxy coating hardening time being made is suitable, mechanical property preferably, can effectively meet construction demand after film forming.
Claims (4)
1. a kind of preparation method of modified aqueous epoxy resin curing agent, it is characterised in that specifically preparation process is：
（1）Regenerated celulose fibre is immersed in 1~2h of stirring in sodium hydroxide solution, filtration washing after 20~24h is stood and does
It is dry, obtain activating and regenerating cellulose fibre；
（2）It will be well mixed after the grinding sieving of activating and regenerating cellulose fibre with triethylene tetramine, at 60~65 DEG C, second be added dropwise
Hexanediol diglycidyl ether and 3~5h of stirring reaction, then epoxy resin is added dropwise, and it is heated to 70~80 DEG C, keeping temperature reaction 3
~4h, then phenyl glycidyl ether is added dropwise, 1~2h of insulation reaction is cooled to after 50~60 DEG C, adds deionized water, then
20~30min of stirring in high-speed shearing emulsion machine is transferred to, modified aqueous epoxy resin curing agent is obtained.
2. a kind of preparation method of modified aqueous epoxy resin curing agent as claimed in claim 1, it is characterised in that step
（2）The triethylene tetramine, ethylene glycol diglycidylether, epoxy resin, the volume of phenyl glycidyl ether and deionized water
Part for 590~600 parts of triethylene tetramines, 150~160 parts of ethylene glycol diglycidylethers, 180~210 parts of epoxy resin, 90~
120 parts of phenyl glycidyl ethers, 100~200 parts of deionized waters.
3. a kind of preparation method of modified aqueous epoxy resin curing agent as claimed in claim 1, it is characterised in that step
（2）The activating and regenerating cellulose fibre consumption is the 0.5~0.8% of triethylene tetramine quality.
4. a kind of preparation method of modified aqueous epoxy resin curing agent as claimed in claim 1, it is characterised in that step
（2）The epoxy resin is one kind in bisphenol A type epoxy resin E-51, E-44 or E-20.
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Cited By (4)
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| CN110577635A (en) * | 2019-09-23 | 2019-12-17 | 固德电材系统（苏州）股份有限公司 | Preparation method and application of water-based epoxy resin curing agent |
| CN112708109A (en) * | 2021-01-11 | 2021-04-27 | 安徽工业大学 | Modified aliphatic polyamine curing agent with long service life and preparation method thereof |
| WO2022212199A1 (en) * | 2021-03-29 | 2022-10-06 | Spero Renewables, Llc | Recyclable and decomposable epoxy resins: compositions, preparation methods and applications in carbon fiber reinforced composites |
| US11891473B2 (en) | 2018-11-21 | 2024-02-06 | The Regents Of The University Of California | Decomposable and recyclable epoxy thermosetting resins |
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