CN109837049A - A kind of preparation method of water-based epoxy resin binder - Google Patents
A kind of preparation method of water-based epoxy resin binder Download PDFInfo
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- CN109837049A CN109837049A CN201910085854.7A CN201910085854A CN109837049A CN 109837049 A CN109837049 A CN 109837049A CN 201910085854 A CN201910085854 A CN 201910085854A CN 109837049 A CN109837049 A CN 109837049A
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Abstract
A kind of preparation method of water-based epoxy resin binder, belongs to field of adhesive technology.The invention solves the technical problems that existing water-based epoxy resin solidfied material internal stress is big and material is brittle.Binder distribution ratio of the invention is easily operated, epoxy resin is used to prepare water-based epoxy resin for matrix, add rubber elastomer and Nanocomposites toughening water-based epoxy resin binder, improve the defect that independent component toughening modifying generates using coordination plasticizing, it is prepared by a certain percentage using water-base emulsion and curing agent, the excellent epoxy adhesive of processability.The obtained water-based epoxy resin binder toughness of the method for the present invention is more preferable, and shear strength is stronger, and peel strength is stronger, and thermal decomposition temperature improves and other performances are not less than solvent epoxy varnish binder.
Description
Technical field
The invention belongs to field of adhesive technology；More particularly to a kind of preparation method of water-based epoxy resin binder
Background technique
As universal thermosetting resin, epoxy resin has good corrosion resistance, caking property, low bulk and electrical isolation
Etc. performances, water-based epoxy resin get the nod and as environmentally friendly system in various fields application, water-based epoxy resin adhesive is
Through the important materials as aerospace science and technology, under the research and development technology of some developed countries, epoxy resin adhesion strength is
Meet the application of space industry, at home and abroad the favor by more and more scientific research personnel.
The good development of numerous patent document summary and inductions aqueous epoxy resins application, nowadays market is for water based epoxy
The performance applications of resin cannot reach the application coverage rate of solvent epoxy varnish binder, because retaining the cementability of epoxy resin
Can, corrosion-and high-temp-resistant energy, the environmental protection of water-based epoxy resin material, non-volatility organic matter in production and use, to actually answering
With the reduction of the injury high degree of personnel, while cost is relatively low；But need to solve water-based epoxy resin solidfied material internal stress
Big and brittle material problem, this problem limit water-based epoxy resin binder in high-new and aerospace science and technology application,
Then increase material application cost.
Summary of the invention
The invention solves the technical problems that existing water-based epoxy resin solidfied material internal stress is big and material is brittle；And it provides
A kind of preparation method of water-based epoxy resin binder, the method for the present invention improve the toughness and mechanical property of binder.
In order to solve the above technical problems, technical scheme is as follows:
A kind of preparation method of water-based epoxy resin binder is completed by following step in the present invention:
Step 1: epoxy resin is mixed with rubber elastomer, 100 DEG C~200 DEG C are heated to, 1~2h of constant temperature is obtained
To modified epoxy；
Step 2: polyether Glycols are added in epoxy resin, wait for that polyether Glycols are all molten when being gradually warmed up to 100 DEG C
Then catalyst potassium peroxydisulfate is added in solution, at 180 DEG C, react 2h, obtain translucent liquid emulsifier；
Step 3: the emulsifier that step 2 obtains is added in the modified epoxy of step 1 acquisition, 60 DEG C~80
30min~60min is stirred at DEG C, deionized water is then added, and is stirred 60min~90min, is obtained Waterborne epoxy resin dispersions；
Step 4: nanoparticle is added, is stirred until homogeneous in the Waterborne epoxy resin dispersions obtained to step 3；
Step 5: curing agent is then added, it is stirred until homogeneous, is heating and curing to get water-based epoxy resin binder is arrived；
Wherein, curing agent described in step 5 is by polyamine compounds, end-capping reagent glycidol ether, epoxy resin and organic
Made of acid.
It further limits, the additional amount of rubber elastomer is the 5%-25% of epoxy resin quality in step 1.
It further limits, epoxy resin described in step 1 is bisphenol A type epoxy resin and/or bisphenol f type epoxy resin；
It is mixed by any ratio when two kinds of combinations；Step 2 and the epoxy resin of curing agent preparation are identical as matrix resin.
It further limits, rubber elastomer described in step 1 is nbr carboxyl terminal (CTBN), terminal hydroxy group butyronitrile rubber
One of glue (HTBN), end hydroxy butadiene (HTPB) or the wherein combination of the two；By any than mixed when two kinds of combinations
It closes.
It further limits, by mole ratio for being (1:1)~(1.2:1) of polyether Glycols and epoxy resin in step 2
Epoxy resin is added in polyether Glycols example.
Further limit, polyether Glycols described in step 2 be polyethylene glycol or polypropylene glycol (it is all can be generated compared with
Other good alcohols chemical agents of polyhydroxy, hydrophilicity)；The additional amount of catalyst described in step 2 is mixed system quality
1%~2%.
It further limits, the additional amount of emulsifier is the 10%~20% of modified epoxy quality in step 3.
It further limits, nanoparticle accounts for the 1%~10% of Waterborne epoxy resin dispersions quality in step 4.
It further limits, nanoparticle described in step 4 is any type of Nano-meter SiO_22Particle or nano-TiO2Grain
Son.
It further limits, nanoparticle described in step 4 is added in the form of silica solution；If the form of addition is that silicon is molten
Glue, silica solution ratio are not higher than 10%, and silica sol particle large specific surface area, particle viscosity is lower, and excessively high and rubber is added in ratio
Elastomer mixing dispersibility may be poor, influences the adhesiveness of water-based epoxy resin.
It further limits, the ratio for being (1.3:1)~(1:1.3) according to the molar ratio of amino and epoxy group in step 5
Curing agent is added.
It further limits, curing agent described in step 5 is prepared in the steps below: first adding glycidol ether
Enter polyamine compounds and carry out end capping reaction, constant temperature stirs at polyamine compounds are 60 DEG C in temperature, and it is sweet that shrink is added dropwise dropwise
Epoxy resin is added in oily ether after end capping reaction, and organic acid is added after ring-opening reaction and carries out salt-forming reaction to get water based epoxy is arrived
Resin curing agent.
It further limits, polyamine compounds described in curing agent preparation process are diethylenetriamine, triethylene tetramine, four
Five amine of ethylene or isophorone diamine；The organic acid is acetic acid (glacial acetic acid) or formic acid or other saturation monoacid；The envelope
Holding agent glycidol ether is benzyl glycidyl ether or butyl glycidyl ether；Polyamine compounds and glycidol ether molar ratio
For 1:1；The additional amount of organic acid is the 1%~2% of mixed system quality；The molar ratio of polyamine compounds and epoxy resin is
2:1。
It further limits, step 5 solidification is solidified 1 hour at 80 DEG C using gradient increased temperature, then is warming up at 120 DEG C solid
Change 2 hours；Or solidification is to be warming up at 100 DEG C 2 hours 1 hour at 80 DEG C, then be warming up at 120 DEG C 1 hour.
It is as follows that water-based epoxy resin emulsifier reaction equation is prepared in the present invention:
The synthesis equation of aqueous epoxy resin curing agent is as follows in the present invention:
Wherein R is represented
Binder component proportion of the invention is easily operated, and epoxy resin is used to prepare water-soluble epoxy resin for matrix,
Rubber elastomer and Nanocomposites toughening water-based epoxy resin binder are added, improves independent component using coordination plasticizing and increases
The tough modified defect generated, is prepared, the excellent epoxy adhesive of processability in proportion using lotion and curing agent.
The obtained water-based epoxy resin binder toughness of the method for the present invention is more preferable, and shear strength is stronger, and peel strength is stronger, heat
Decomposition temperature improves and other performances are not less than solvent epoxy varnish binder.
The method of the present invention high-efficiency environment friendly.
The method of the present invention does not reduce the mechanical and physical performance of water-based epoxy resin while epoxy resin toughness increases, and glues
It is strong to connect performance, comprehensive performance extends concrete application due to solvent epoxy varnish.
Detailed description of the invention
Fig. 1 is EP solidfied material, CTBN/EP solidfied material and SiO2The INFRARED SPECTRUM of/CTBN modified water-base epoxy resin cured product
Figure；A curve is water-based epoxy resin solidfied material in Fig. 1, and b curve is CTBN modified water-base epoxy resin cured product, and c curve is to receive
Rice SiO2/ CTBN water-based epoxy resin solidfied material, d curve are silica solution/CTBN water-based epoxy resin solidfied materials；
Fig. 2 is the water-based epoxy resin binder picture of different ratio；Fig. 2 (a) is the mass fraction of CTBN in embodiment 1
It is 20%, silica solution form SiO2Mass fraction is 5%；Fig. 2 (b) is that the mass fraction of HTBN in embodiment 2 is 20%, nanometer
SiO2Mass fraction is 3%；Fig. 2 (c) is that the mass fraction of CTBN in embodiment 3 is 20%, Nano-meter SiO_22Mass fraction is 3%.
Specific embodiment
Embodiment 1: a kind of preparation method of water-based epoxy resin binder is completed by following step in the present embodiment
:
Step 1: 25g bisphenol A type epoxy resin E44 is mixed with 5g nbr carboxyl terminal (CTBN), it is heated to
150 DEG C, heating stirring 1h obtains modified epoxy；
Step 2: 3.96g bisphenol A type epoxy resin E44 is added in 40g polyethylene glycol, it is gradually warmed up to 100 DEG C of poly- second
Glycol is completely dissolved, and 0.5g potassium peroxydisulfate is then added, and at 180 DEG C, is reacted 2h, is obtained the translucent emulsifying liquid of yellow
Agent；
Step 3: the emulsifier (additive amount is modified epoxy mass fraction 20%) that 5g step 2 obtains is added to step
In rapid one modified epoxy obtained, 30min is stirred at 60 DEG C, 8ml deionized water is then added, and is stirred 60min, is obtained
Waterborne epoxy resin dispersions；
Step 4: silica solution is added, and (silica solution form introduces nanometer in the Waterborne epoxy resin dispersions obtained to step 3
SiO2The mass fraction of particle is 1%, 2%, 3%, 4% or 5%), is stirred until homogeneous；
Step 5: being then that curing agent is added in 1:1 according to the molar ratio of amino and epoxy group, stir evenly, at 80 DEG C
It is heating and curing 1 hour, then is warming up at 120 DEG C 2 hours to get to water-based epoxy resin binder；
Wherein, curing agent described in step 5 is prepared in the steps below: 13g diethylenetriamine and 8g benzyl are contracted
Water glycerin ether carries out end capping reaction respectively, and benzyl is added dropwise dropwise and shrinks for heated at constant temperature at being 60 DEG C in temperature by diethylenetriamine
10g epoxy resin is added in glycerin ether after being added dropwise, to ring-opening reaction after, obtain mixed system, be added 3g glacial acetic acid into
Row salt-forming reaction to get arrive curing agent.
After tested, water-based epoxy resin binder performance index in the present embodiment: when CTBN mass fraction be 20%, silicon
Solation introduces SiO2When mass fraction is 5%, the toughening effect of water-based epoxy resin binder is best, and shear strength reaches
37.6Mpa, peel strength 4.67N mm-1, thermal decomposition temperature is promoted to 320 DEG C.
Embodiment 2: a kind of preparation method of water-based epoxy resin binder is completed by following step in the present embodiment
:
Step 1: 25g bisphenol A type epoxy resin E51 is mixed with 5g hydroxy'terminated butadiene nitrile rubber (HTBN), it is heated to
150 DEG C, heating stirring 1h obtains modified epoxy；
Step 2: 4g bisphenol A type epoxy resin E51 is added in 40g polyethylene glycol, it is gradually warmed up to 100 DEG C of poly- second two
Alcohol is completely dissolved, and 0.5g potassium peroxydisulfate is then added, and at 180 DEG C, is reacted 3h, is obtained the translucent liquid emulsifier of yellow；
Step 3: the emulsifier (additive amount is modified epoxy mass fraction 20%) that 5g step 2 obtains is added to step
In rapid one modified epoxy obtained, 30min is stirred at 60 DEG C, 8ml deionized water is then added, and is stirred 60min, is obtained
Waterborne epoxy resin dispersions；
Step 4: Nano-meter SiO_2 is added in the Waterborne epoxy resin dispersions obtained to step 32Particle (Nano-meter SiO_22Particle
Mass fraction is 1%, 2%, 3%, 4% or 5%), is stirred evenly；
Step 5: being then that curing agent is added in 1:1 according to the molar ratio of amino and epoxy group, stir evenly, at 80 DEG C
It is heating and curing 1 hour, then is warming up at 120 DEG C 2 hours to get to water-based epoxy resin binder；
Wherein, curing agent described in step 5 is prepared in the steps below: 13g diethylenetriamine and 8g benzyl are contracted
Water glycerin ether carries out end capping reaction respectively, and benzyl is added dropwise dropwise and shrinks for heated at constant temperature at being 60 DEG C in temperature by diethylenetriamine
10g epoxy resin is added in glycerin ether after being added dropwise, to ring-opening reaction after, obtain mixed system, be added 3g glacial acetic acid into
Row salt-forming reaction to get arrive curing agent.
After tested, water-based epoxy resin binder performance index in the present embodiment: when HTBN mass fraction be 20%, receive
Rice SiO2When mass fraction is 3%, the toughening effect of water-based epoxy resin binder is best, and shear strength reaches 28.9Mpa, stripping
From intensity 3.98N mm-1, thermal decomposition temperature is promoted to 312 DEG C.
Embodiment 3: a kind of preparation method of water-based epoxy resin binder is completed by following step in the present embodiment
:
Step 1: 25g bisphenol A type epoxy resin E44 is mixed with 5g nbr carboxyl terminal (CTBN), it is heated to
120 DEG C, heating stirring 2h obtains modified epoxy；
Step 2: 3.96g bisphenol A type epoxy resin E44 is added in 40g polyethylene glycol, it is gradually warmed up to 100 DEG C of poly- second
Glycol is completely dissolved, and 0.5g potassium peroxydisulfate is then added, and at 160 DEG C, is reacted 3h, is obtained liquid emulsifier；
Step 3: the emulsifier that 5g step 2 obtains is added in the modified epoxy of step 1 acquisition, at 60 DEG C
30min is stirred, 8ml deionized water is then added, 60min is stirred, obtains Waterborne epoxy resin dispersions；
Step 4: Nano-meter SiO_2 is added in the Waterborne epoxy resin dispersions obtained to step 32Particle (Nano-meter SiO_22Particle
Mass fraction is 1%, 2%, 3%, 4% or 5%), is stirred evenly；
Step 5: being then that curing agent is added in 1:1 according to the molar ratio of amino and epoxy group, stir evenly, at 80 DEG C
It is heating and curing 1 hour, is warming up at 100 DEG C 2 hours, then be warming up to 1 hour at 120 DEG C and binded to get to water-based epoxy resin
Agent；
Wherein, curing agent described in step 5 is prepared in the steps below: 15g triethylene tetramine and 7g butyl are contracted
Water glycerin ether carries out end capping reaction respectively, and butyl is added dropwise dropwise and shrinks for heated at constant temperature at being 60 DEG C in temperature by triethylene tetramine
10g epoxy resin is added in glycerin ether after being added dropwise, to ring-opening reaction after, obtain mixed system, be added 3g glacial acetic acid into
Row salt-forming reaction to get arrive curing agent.
After tested, water-based epoxy resin binder performance index in the present embodiment: when CTBN mass fraction be 20%, receive
Rice SiO2When mass fraction is 3%, the toughening effect of water-based epoxy resin binder is best, and shear strength reaches 27.6Mpa, stripping
From intensity 3.78N mm-1, thermal decomposition temperature is promoted to 313 DEG C.
Product is detected, as a result as illustrated in fig. 1 and 2,
As shown in Figure 1, substance completion of cure is prepared known to four curves, the characteristic peak of epoxy resin is all it is obvious that b in a
The characteristic peak of middle C=O ,-CH=CH- are provided with, and-OH vibration peak enhancing explanation introduces SiO in c, d2, curvilinear motion explanation change
Property water-based epoxy resin simultaneously has not been changed resin chemical structure.
As shown in Figure 2, water-based epoxy resin binder apparent viscosity obviously increases in a, b, SiO in c2With the addition of CTBN
Uniformly and glue is apparent pure smooth, clean and tidy environmental protection.
Claims (10)
1. a kind of preparation method of water-based epoxy resin binder, it is characterised in that the preparation method is complete by following step
At:
Step 1: epoxy resin is mixed with rubber elastomer, 100 DEG C~200 DEG C are heated to, 1~2h of constant temperature is changed
Property epoxy resin；
Step 2: polyether Glycols are added in epoxy resin, wait for that polyether Glycols all dissolve when being gradually warmed up to 100 DEG C,
Then catalyst potassium peroxydisulfate is added, at 180 DEG C, reacts 2h, obtains translucent liquid emulsifier；
Step 3: the emulsifier that step 2 obtains is added in the modified epoxy of step 1 acquisition, at 60 DEG C~80 DEG C
30min~60min is stirred, deionized water is then added, 60min~90min is stirred, obtains Waterborne epoxy resin dispersions；
Step 4: nanoparticle is added, is stirred until homogeneous in the Waterborne epoxy resin dispersions obtained to step 3；
Step 5: curing agent is then added, it is stirred until homogeneous, is heating and curing to get water-based epoxy resin binder is arrived；
Wherein, curing agent described in step 5 is by polyamine compounds, end-capping reagent glycidol ether, epoxy resin and organic acid system
At.
2. a kind of preparation method of water-based epoxy resin binder according to claim 1, it is characterised in that in step 1
The additional amount of rubber elastomer is the 5%-25% of epoxy resin quality.
3. a kind of preparation method of water-based epoxy resin binder according to claim 1, it is characterised in that step 1 institute
Stating epoxy resin is bisphenol A type epoxy resin and/or bisphenol f type epoxy resin；The asphalt mixtures modified by epoxy resin of step 2 and curing agent preparation
Rouge is identical as matrix resin；Rubber elastomer described in step 1 is nbr carboxyl terminal (CTBN), hydroxy'terminated butadiene nitrile rubber
(HTBN), one of end hydroxy butadiene (HTPB) or the wherein combination of the two.
4. a kind of preparation method of water-based epoxy resin binder according to claim 1, it is characterised in that in step 2
It is that (1:1)~(1.2:1) will be in epoxy resin addition polyether Glycols by the molar ratio of polyether Glycols and epoxy resin；Step
Two polyether Glycols are polyethylene glycol or polypropylene glycol；The additional amount of catalyst described in step 2 is mixed system quality
1%~2%.
5. a kind of preparation method of water-based epoxy resin binder according to claim 1, it is characterised in that in step 3
The additional amount of emulsifier is the 10%~20% of modified epoxy quality.
6. a kind of preparation method of water-based epoxy resin binder according to claim 1, it is characterised in that in step 4
Nanoparticle accounts for the 1%~10% of Waterborne epoxy resin dispersions quality；The nanoparticle is Nano-meter SiO_22Particle or nano-TiO2
Particle.
7. a kind of preparation method of water-based epoxy resin binder according to claim 1, it is characterised in that in step 5
It is that curing agent is added in (1.3:1)~(1:1.3) according to the molar ratio of amino and epoxy group.
8. a kind of preparation method of water-based epoxy resin binder according to claim 1, it is characterised in that step 5 institute
It states curing agent to be prepared in the steps below: polyamine compounds first is added in glycidol ether and carry out end capping reaction, it is more
Constant temperature stirs at aminated compounds is 60 DEG C in temperature, and glycidol ether is added dropwise dropwise, epoxy resin is added after end capping reaction,
Organic acid is added after ring-opening reaction and carries out salt-forming reaction to get water-based epoxy resin curing agent is arrived.
9. a kind of preparation method of water-based epoxy resin binder according to claim 8, it is characterised in that curing agent system
The polyamine compounds are diethylenetriamine, triethylene tetramine, tetraethylenepentamine or isophorone diamine during standby；It is described
Organic acid is acetic acid (glacial acetic acid) or formic acid or other saturation monoacid；The end-capping reagent glycidol ether is benzyl glycidol
Ether or butyl glycidyl ether；Polyamine compounds and glycidol ether molar ratio are 1:1；The additional amount of organic acid is mixture
It is the 1%~2% of quality；The molar ratio of polyamine compounds and epoxy resin is 2:1.
10. a kind of preparation method of water-based epoxy resin binder according to claim 8, it is characterised in that step 5 is solid
Change and solidified 1 hour at 80 DEG C using gradient increased temperature, then is warming up at 120 DEG C and solidifies 2 hours；Or solidification is 1 at 80 DEG C
Hour, it is warming up at 100 DEG C 2 hours, then be warming up at 120 DEG C 1 hour.
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| CN110820345A (en) * | 2019-12-02 | 2020-02-21 | 安徽宜民服饰股份有限公司 | Treatment process of shrink-proof cotton fabric |
| CN112111067A (en) * | 2020-09-24 | 2020-12-22 | 邓会群 | Modified epoxy resin and preparation method thereof, emulsified modified epoxy resin and preparation method and application thereof, and sandwich adhesive for aluminum honeycomb core |
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