CN101659741A - Epoxy resin toughening curing agent and preparation method thereof - Google Patents
Epoxy resin toughening curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN101659741A CN101659741A CN200910167811A CN200910167811A CN101659741A CN 101659741 A CN101659741 A CN 101659741A CN 200910167811 A CN200910167811 A CN 200910167811A CN 200910167811 A CN200910167811 A CN 200910167811A CN 101659741 A CN101659741 A CN 101659741A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- epoxy
- ether
- preparation
- curing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Epoxy Resins (AREA)
Abstract
An epoxy resin toughening curing agent is prepared according to the following process steps: (1) preparation of a terminal amino group midbody, wherein the mol ratio between saturated aliphatic polyamine and epoxy resin is 2:1-4:1, the saturated aliphatic polyamine is heated to the temperature of 50-80 DEG C, then a epoxy resin solution is dripped into a reaction vessel for polymerization reactionfor 2.5-5.5 hours at the temperature of 50-80 DEG C, the unreacted saturated aliphatic polyamine is removed by means of reduced pressure distillation after the reaction is finished, and a terminal amino group midbody solution is obtained; and (2) the preparation of the epoxy resin toughening curing agent, wherein the mol ratio between the terminal amino group midbody and epoxy oleate is 1:2, theepoxy oleate is dripped into the reaction vessel containing the terminal amino group midbody solution for polymerization reaction for 2-4 hours at 50-80 DEG C, and the epoxy resin toughening curing agent is obtained. The toughening curing agent can remarkably improve the impact strength of cured epoxy resin without reducing the thermal performance thereof.
Description
Technical field
The invention belongs to the epoxy curing agent field, particularly a kind of based on greasy epoxy resin roughening and curing agent and preparation method thereof.
Background technology
Resins, epoxy is a kind of universal thermosetting resin, has hindered application more widely but solidify defectives such as the back existence is crisp, poor impact resistance because of it.For this reason, the research to epoxy resin roughening has become one of focus direction of Resins, epoxy research.
Existing epoxy resin roughening and curing agent, have in the traditional epoxy curing agent molecular structure of fatty amine, cycloaliphatic amines and anhydrides and to introduce soft segments such as flexible long carbochain, polyoxyethylene or polyoxypropylene by modification, and adopt flexible polymer based epoxy resin curing agent such as polymeric amide etc.Though use above-mentioned solidifying agent all to obtain good effect at aspects such as the mechanics of cured resin and physical and chemical performances, they are to be starting raw material with the oil.Along with rising suddenly and sharply of International Crude Oil, the continuous exhaustion of petroleum resources is sought reproducible oil replacement product and has been caused global extensive concern.
Over past ten years, utilize reproducible epoxidized vegetable oil fat, mix methyl soyate (EMS) and allyl ester (EAS) etc. and epoxy blend as epoxidised soybean oil (ESO) and by the epoxidation that forms after the transesterify, caused the interest of Many researchers then with traditional solidifying agent solidified research.As in bisphenol A-type bifunctional Resins, epoxy/anhydride-cured system, adding part epoxidised soybean oil and epoxidation linseed oil (ELO) replacement Resins, epoxy, can effective toughness reinforcing cured resin, but the second-order transition temperature Tg of the Resins, epoxy after toughness reinforcing and cross-linking density reduce, and mechanical property etc. faster descend with the increase of epoxidized oil add-on.This is because the epoxy group(ing) in the epoxidized vegetable oil structure mediates, its reactive behavior is lower than Resins, epoxy, can not participate in curing reaction fully, make the part epoxidized vegetable oil still only play a part softening agent, so the thermal characteristics of curing system and mechanical properties decrease.Described ESO, EMS and EAS are reacted the formation prepolymer as epoxy curing agent with amine curing agent in advance, when guaranteeing toughening effect, the thermal characteristics of curing system and mechanical properties decrease can further reduce, but still can not guarantee unaffected (1.S.Kar and A.K.Banthia.Epoxy Resin Modified with Epoxidized Soybean Rubber.Materialsand Manufacturing Processes.2004,19 (3): 459-474; 2.Jiang Zhu, et al.Curing andMechanical Characterization of a Soy-Based Epoxy Resin System.Journal of AppliedPolymer Science.2004,91:3513-3518).
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of neo-epoxy resin roughening and curing agent and preparation method thereof is provided, this kind solidifying agent substitutes part petroleum base raw material with renewable resources epoxyoleic acid fat, under the situation of not adding other toughner, can make cured epoxy resin when shock strength improves, keep good thermal characteristics.
Epoxy resin roughening and curing agent of the present invention, its structural formula is as follows:
In the said structure formula, R is-CH
3,-C
2H
5, ,-C
4H
9,-C
8H
17In a kind of, n is 1 or 2 or 3.
The preparation method of epoxy resin roughening and curing agent of the present invention adopts excess fat family's polyamine and Resins, epoxy to react at a lower temperature, forms the prepolymer of end amido---end amido intermediate.Then, above-mentioned prepolymer is carried out modification with the Epoxy oil acid esters to its terminal primary amine base, introduce flexible carbochain in the solidifying agent molecular structure, its processing step is as follows:
(1) preparation of end amido intermediate
Containing at least 5 reactive amines with per molecule, to belong to the representative examples of saturated aliphatic polyamine of hydrogen atom and epoxy functionalities be that 2 Resins, epoxy is raw material, and the mol ratio of described representative examples of saturated aliphatic polyamine and described Resins, epoxy is 2: 1～4: 1, and Principles of Polymerization are formula as follows:
In the following formula, n is 1 or 2 or 3, and m is an arbitrary value between the 2-4.
Preparation manipulation: in reaction vessel and another container, be respectively charged into a kind of solvent, described representative examples of saturated aliphatic polyamine is put into reaction vessel form representative examples of saturated aliphatic polyamine solution, described Resins, epoxy is put into another container form epoxy resin solution, the amount of solvent is exceeded with the requirement that the viscosity of formed solution meets stirring; Representative examples of saturated aliphatic polyamine solution is heated to 50 ℃～80 ℃, under agitation epoxy resin solution is splashed into reaction vessel then, after epoxy resin solution is splashed into reaction vessel fully, under agitation continued polyreaction 2.5 hours～5.5 hours in 50 ℃～80 ℃, after reaction finishes, remove unreacted representative examples of saturated aliphatic polyamine by underpressure distillation, promptly obtain end amido midbody solution;
(2) preparation of epoxy resin roughening and curing agent
End amido midbody solution and Epoxy oil acid esters with step (1) preparation are that raw material is (excessive as end amido midbody solution viscosity, can add solvent makes viscosity meet the stirring requirement), the mol ratio of end amido intermediate and Epoxy oil acid esters is 1: 2, to hold amido intermediate and Epoxy oil acid esters to carry out end capping, reaction principle is formula as follows:
In the following formula, R is-CH
3,-C
2H
5, ,-C
4H
9,-C
8H
17In a kind of, n is 1 or 2 or 3.
Preparation manipulation: when the temperature that the question response container is adorned end amido midbody solution is 50 ℃～80 ℃, under agitation the Epoxy oil acid esters is splashed into reaction vessel, after the Epoxy oil acid esters is splashed into reaction vessel fully, under agitation continued polyreaction 2 hours～4 hours in 50 ℃～80 ℃, reaction is reduced to room temperature (indoor natural temperature) after finishing, with the reaction product standing demix, separate the lower floor's product that obtains and be epoxy resin roughening and curing agent.
In the aforesaid method, preferably under protection of inert gas, described representative examples of saturated aliphatic polyamine is put into reaction vessel and form representative examples of saturated aliphatic polyamine solution.
In the preparation process of described end amido intermediate, the dropping time of epoxy resin solution is 1.5 hours～2.5 hours; In the preparation process of described epoxy resin roughening and curing agent, the dropping time of Epoxy oil acid esters is 2 hours～4 hours.
In the aforesaid method, described representative examples of saturated aliphatic polyamine is at least a in two inferior ethene triamines, Sanya ethene tetramine, four inferior ethene five amine; The preferred epoxy functionalities of described Resins, epoxy is 2 liquid epoxies (can be any structure).
In the aforesaid method, described Epoxy oil acid esters is a kind of in epoxyoleic acid methyl esters, epoxyoleic acid ethyl ester, epoxyoleic acid butyl ester, the epoxyoleic acid monooctyl ester.
In the aforesaid method, described solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol list propyl ether, a kind of in the dipropylene glycol monobutyl ether.
The present invention has following beneficial effect:
1, because the raw material of selecting for use---the Epoxy oil acid esters is not the epoxide of grease by the various mixed aliphatic esters of transesterify formation, there are not fatty acid glyceryl ester that transesterification reaction does not take place and the polyunsaturated fatty acid ester that can only play plastification in the raw material, owing in the epoxyoleic acid ester molecular structure, introduced the longer ester group of carbochain, promptly longer flexible chain, therefore, use solidifying agent solidified Resins, epoxy shock strength of the present invention to significantly improve, and thermal characteristics and Young's modulus influenced hardly (seeing embodiment 7).
2, the Epoxy oil acid esters is a vegetables oil, is renewable resources, replaces the petroleum base raw material to have extensive, the with low cost advantage of raw material sources with the Epoxy oil acid esters.
3, the method for the invention synthesis technique is simple, and is easy and simple to handle, is convenient to suitability for industrialized production.
Description of drawings
Fig. 1 is the infrared spectrogram (FT-IR) of the end amido intermediate among the present invention;
Fig. 2 is the infrared spectrogram (FT-IR) of epoxy resin roughening and curing agent of the present invention;
Fig. 3 is to use impact fracture face scanning electron microscope (SEM) photo of traditional solidifying agent (prepolymer of polyamines and Resins, epoxy) solidified Resins, epoxy;
Fig. 4 is to use impact fracture face scanning electron microscope (SEM) photo of the prepared roughening and curing agent solidified Resins, epoxy of present patent application embodiment 1;
Fig. 5 is to use impact fracture face scanning electron microscope (SEM) photo of the prepared roughening and curing agent solidified Resins, epoxy of present patent application embodiment 6.
Embodiment
In order better to understand content of the present invention, below by embodiment the present invention is further described, but the scope of protection of present invention is not limited to the described scope of embodiment.
Among following embodiment 1～embodiment 6, reaction vessel is a 1000mL four-hole glass reaction bottle, on this four-hole glass reaction bottle reflux condensing tube, thermometer and stirring rake is housed, and described stirring rake is an anchor formula stirring arm, stirring velocity 400rpm; Type of heating is the external placed type constant temperature oil bath.
The processing step of present embodiment is as follows:
(1) preparation of end amido intermediate
With diethylenetriamine and Resins, epoxy E-51 is raw material, and described diethylenetriamine is 0.6 mole, and described Resins, epoxy E-51 is 0.25 mole;
The 100mL ethylene glycol monomethyl ether solvent of in reaction vessel, packing into, under the drying nitrogen protection, 0.6 mole diethylenetriamine is put into reaction vessel form diethylenetriamine solution, the 50mL ethylene glycol monomethyl ether solvent of packing in another container is put into another container with 0.25 mole of Resins, epoxy E-51 and is formed Resins, epoxy E-51 solution;
The temperature of diethylenetriamine solution rises to 60 ℃ in the question response container, under agitation described Resins, epoxy E-51 solution is at the uniform velocity splashed into reaction vessel, the dropping time is 1.5 hours, after Resins, epoxy E-51 solution is splashed into reaction vessel fully, under agitation continued polyreaction 2.5 hours in 60 ℃, after reaction finishes, temperature in the reaction vessel is risen to 150 ℃, remove unreacted diethylenetriamine by underpressure distillation, promptly obtain diethylenetriamine-Resins, epoxy E-51 end amido midbody solution, in the described end amido midbody solution, diethylenetriamine-Resins, epoxy E-51 end amido intermediate is 0.25 mole.
(2) preparation of epoxy resin roughening and curing agent
With step (1) diethylenetriamine that obtained-Resins, epoxy E-51 end amido midbody solution and 0.5 mole of epoxyoleic acid methyl esters is that raw material is (excessive as end amido midbody solution viscosity, can add the ethylene glycol monomethyl ether solvent makes viscosity meet the stirring requirement), the temperature that the question response container is adorned diethylenetriamine-Resins, epoxy E-51 end amido midbody solution is reduced to 65 ℃, under agitation 0.5 mole of epoxyoleic acid methyl esters is at the uniform velocity splashed into reaction vessel, the dropping time is 4 hours, after the epoxyoleic acid methyl esters is splashed into reaction vessel fully, under agitation continue reaction 2 hours in 65 ℃, reaction is reduced to room temperature after finishing, with the reaction product standing demix, separate the lower floor's product that obtains and be epoxy resin roughening and curing agent (color is lurid transparent liquid).Its general structure is as described in the summary of the invention part, and wherein R is-CH
3, n is 1.
The infrared spectrogram of diethylenetriamine-Resins, epoxy E-51 end amido intermediate that present embodiment is prepared as shown in Figure 1.Among Fig. 1, at 1608cm
-1, 1581cm
-1, 1510cm
-1, 1459cm
-1The peak that the place occurs is the skeletal vibration charateristic avsorption band of Resins, epoxy, 830cm
-1Place and 770cm
-1Two peaks at place show that phenyl ring is a contraposition disubstituted benzenes ring, and the epoxy group(ing) characteristic peak (915cm of Resins, epoxy
-1) the basic disappearance.3300～3500cm
-1The interval is the charateristic avsorption band interval of primary amine and secondary amine, at 3351cm
-1And 3291cm
-1It is bimodal that the feature of Fermi resonance appears in the place, is the terminal primary amine group of diethylenetriamine-Resins, epoxy E-51 affixture.
The infrared spectra of the epoxy resin roughening and curing agent that present embodiment is prepared as shown in Figure 2.In Fig. 2,3300～3500cm
-1Between the feature biabsorption peak of terminal primary amine group disappear.Can think to have primary amine group hardly in the product, and among Fig. 2 at 1736cm
-1And 1733cm
-1Tangible ester bond-COO-absorption peak has appearred in the place.Illustrate in terminal primary amine group on diethylenetriamine-Resins, epoxy E-51 affixture and the epoxyoleic acid methyl esters epoxide group reaction has taken place, and reaction is more complete.
The product of following examples preparation has infared spectrum substantially the same manner as Example 1, will no longer specifically describe in detail below.
The processing step of present embodiment is as follows:
(1) preparation of end amido intermediate
With triethylene tetramine and Resins, epoxy E-51 is raw material, and described triethylene tetramine is 1.0 moles, and described Resins, epoxy E-51 is 0.25 mole;
The 100mL propylene glycol monomethyl ether solvent of in reaction vessel, packing into, under the drying nitrogen protection, 1.0 moles triethylene tetramine is put into reaction vessel form triethylene tetramine solution, the 50mL propylene glycol monomethyl ether solvent of packing in another container is put into another container with 0.25 mole of Resins, epoxy E-51 and is formed Resins, epoxy E-51 solution;
The temperature of triethylene tetramine solution rises to 50 ℃ in the question response container, under agitation described Resins, epoxy E-51 solution is at the uniform velocity splashed into reaction vessel, the dropping time is 2.5 hours, after Resins, epoxy E-51 solution is splashed into reaction vessel fully, under agitation continued polyreaction 5.5 hours in 50 ℃, after reaction finishes, temperature in the reaction vessel is risen to 180 ℃, remove unreacted triethylene tetramine by underpressure distillation, promptly obtain triethylene tetramine-Resins, epoxy E-51 end amido midbody solution, in the described end amido midbody solution, triethylene tetramine-Resins, epoxy E-51 end amido intermediate is 0.25 mole.
(2) preparation of epoxy resin roughening and curing agent
With step (1) triethylene tetramine that obtained-Resins, epoxy E-51 end amido midbody solution and 0.5 mole of epoxyoleic acid methyl esters is that raw material is (excessive as end amido midbody solution viscosity, can add the propylene glycol monomethyl ether solvent makes viscosity meet the stirring requirement), the temperature that the question response container is adorned triethylene tetramine-Resins, epoxy E-51 end amido midbody solution is reduced to 50 ℃, under agitation 0.5 mole of epoxyoleic acid methyl esters is at the uniform velocity splashed into reaction vessel, the dropping time is 4 hours, after the epoxyoleic acid methyl esters is splashed into reaction vessel fully, under agitation continue reaction 4 hours in 50 ℃, reaction is reduced to room temperature after finishing, with the reaction product standing demix, separate the lower floor's product that obtains and be epoxy resin roughening and curing agent (color is lurid transparent liquid).Its general structure is as described in the summary of the invention part, and wherein R is-CH
3, n is 2.
Embodiment 3
(1) preparation of end amido intermediate
With diethylenetriamine and epoxy resin E-44 is raw material, and described diethylenetriamine is 0.6 mole, and described epoxy resin E-44 is 0.25 mole;
The 100mL propylene glycol monobutyl ether solvent of in reaction vessel, packing into, under the drying nitrogen protection, 0.6 mole diethylenetriamine is put into reaction vessel form diethylenetriamine solution, the 50mL propylene glycol monobutyl ether solvent of packing in another container is put into another container with 0.25 mole of epoxy resin E-44 and is formed epoxy resin E-44 solution;
The temperature of diethylenetriamine solution rises to 80 ℃ in the question response container, under agitation described epoxy resin E-44 solution is at the uniform velocity splashed into reaction vessel, the dropping time is 1.5 hours, after epoxy resin E-44 solution is splashed into reaction vessel fully, under agitation continued polyreaction 2.5 hours in 80 ℃, after reaction finishes, temperature in the reaction vessel is risen to 150 ℃, remove unreacted diethylenetriamine by underpressure distillation, promptly obtain diethylenetriamine-epoxy resin E-44 end amido midbody solution, in the described end amido midbody solution, diethylenetriamine-epoxy resin E-44 end amido intermediate is 0.25 mole.
(2) preparation of epoxy resin roughening and curing agent
With step (1) diethylenetriamine that obtained-epoxy resin E-44 end amido midbody solution and 0.5 mole of epoxyoleic acid monooctyl ester is that raw material is (excessive as end amido midbody solution viscosity, can add the propylene glycol monobutyl ether solvent makes viscosity meet the stirring requirement), the temperature that the question response container is adorned diethylenetriamine-epoxy resin E-44 end amido midbody solution is reduced to 80 ℃, under agitation 0.5 mole of epoxyoleic acid monooctyl ester is at the uniform velocity splashed into reaction vessel, the dropping time is 2 hours, after the epoxyoleic acid methyl esters is splashed into reaction vessel fully, under agitation continue reaction 2 hours in 80 ℃, reaction is reduced to room temperature after finishing, with the reaction product standing demix, separate the lower floor's product that obtains and be epoxy resin roughening and curing agent (color is lurid transparent liquid).Its general structure is as described in the summary of the invention part, and wherein R is-C
8H
17, n is 1.
Embodiment 4
The processing step of present embodiment is as follows:
(1) preparation of end amido intermediate
With triethylene tetramine and epoxy resin E-44 is raw material, and described triethylene tetramine is 0.5 mole, and described epoxy resin E-44 is 0.25 mole;
The 100mL dipropylene glycol monomethyl ether solvent of in reaction vessel, packing into, under the drying nitrogen protection, 0.5 mole triethylene tetramine is put into reaction vessel form triethylene tetramine solution, the 50mL dipropylene glycol monomethyl ether solvent of packing in another container is put into another container with 0.25 mole of epoxy resin E-44 and is formed epoxy resin E-44 solution;
The temperature of triethylene tetramine solution rises to 60 ℃ in the question response container, under agitation described epoxy resin E-44 solution is at the uniform velocity splashed into reaction vessel, the dropping time is 2.0 hours, after epoxy resin E-44 solution is splashed into reaction vessel fully, under agitation continued polyreaction 3.5 hours in 60 ℃, after reaction finishes, temperature in the reaction vessel is risen to 180 ℃, remove unreacted triethylene tetramine by underpressure distillation, promptly obtain triethylene tetramine-epoxy resin E-44 end amido midbody solution, in the described end amido midbody solution, triethylene tetramine-epoxy resin E-44 end amido intermediate is 0.25 mole.
(2) preparation of epoxy resin roughening and curing agent
With step (1) triethylene tetramine that obtained-epoxy resin E-44 end amido midbody solution and 0.5 mole of epoxyoleic acid methyl esters is that raw material is (excessive as end amido midbody solution viscosity, can add dipropylene glycol monomethyl ether makes viscosity meet the stirring requirement), the temperature that the question response container is adorned triethylene tetramine-epoxy resin E-44 end amido midbody solution is reduced to 65 ℃, under agitation 0.5 mole of epoxyoleic acid methyl esters is at the uniform velocity splashed into reaction vessel, the dropping time is 3 hours, after the epoxyoleic acid methyl esters is splashed into reaction vessel fully, under agitation continue reaction 2 hours in 65 ℃, reaction is reduced to room temperature after finishing, with the reaction product standing demix, separate the lower floor's product that obtains and be epoxy resin roughening and curing agent (color is lurid transparent liquid).Its general structure is as described in the summary of the invention part, and wherein R is-CH
3, n is 2.
Embodiment 5
The processing step of present embodiment is as follows:
(1) preparation of end amido intermediate
With triethylene tetramine and epoxy resin E-44 is raw material, and described triethylene tetramine is 0.55 mole, and described epoxy resin E-44 is 0.25 mole;
The 100mL propylene glycol monobutyl ether solvent of in reaction vessel, packing into, under the drying nitrogen protection, 0.55 mole triethylene tetramine is put into reaction vessel form triethylene tetramine solution, the 50mL propylene glycol monobutyl ether solvent of packing in another container is put into another container with 0.25 mole of epoxy resin E-44 and is formed epoxy resin E-44 solution;
The temperature of triethylene tetramine solution rises to 60 ℃ in the question response container, under agitation described epoxy resin E-44 solution is at the uniform velocity splashed into reaction vessel, the dropping time is 2.5 hours, after epoxy resin E-44 solution is splashed into reaction vessel fully, under agitation continued polyreaction 4.5 hours in 60 ℃, after reaction finishes, temperature in the reaction vessel is risen to 200 ℃, remove unreacted triethylene tetramine by underpressure distillation, promptly obtain triethylene tetramine-epoxy resin E-44 end amido midbody solution, in the described end amido midbody solution, triethylene tetramine-epoxy resin E-44 end amido intermediate is 0.25 mole.
(2) preparation of epoxy resin roughening and curing agent
With step (1) triethylene tetramine that obtained-epoxy resin E-44 end amido midbody solution and 0.5 mole of epoxyoleic acid butyl ester is that raw material is (excessive as end amido midbody solution viscosity, can add propylene glycol monobutyl ether makes viscosity meet the stirring requirement), the temperature that the question response container is adorned triethylene tetramine-epoxy resin E-44 end amido midbody solution is reduced to 65 ℃, under agitation 0.5 mole of epoxyoleic acid methyl esters is at the uniform velocity splashed into reaction vessel, the dropping time is 3.5 hours, after the epoxyoleic acid methyl esters is splashed into reaction vessel fully, under agitation continue reaction 2 hours in 65 ℃, reaction is reduced to room temperature after finishing, with the reaction product standing demix, separate the lower floor's product that obtains and be epoxy resin roughening and curing agent (color is lurid transparent liquid).Its general structure is as described in the summary of the invention part, and wherein R is-C
4H
9, n is 2.
Embodiment 6
The processing step of present embodiment is as follows:
(1) preparation of end amido intermediate
With diethylenetriamine, tetraethylene pentamine and Resins, epoxy E-51 is raw material, and described diethylenetriamine is 0.4 mole, and described tetraethylene pentamine is 0.2 mole, and described Resins, epoxy E-51 is 0.25 mole;
The 100mL diethylene glycol monomethyl ether solvent of in reaction vessel, packing into, under the drying nitrogen protection, 0.4 mole diethylenetriamine and 0.2 mole of tetraethylene pentamine are put into reaction vessel formation diethylenetriamine and tetraethylene pentamine mixing solutions, the 50mL diethylene glycol monomethyl ether solvent of packing in another container is put into another container with 0.25 mole of Resins, epoxy E-51 and is formed Resins, epoxy E-51 solution;
The temperature of diethylenetriamine and tetraethylene pentamine mixing solutions rises to 60 ℃ in the question response container, under agitation described Resins, epoxy E-51 solution is at the uniform velocity splashed into reaction vessel, the dropping time is 1.5 hours, after Resins, epoxy E-51 solution is splashed into reaction vessel fully, under agitation continued polyreaction 2.5 hours in 60 ℃, after reaction finishes, temperature in the reaction vessel is risen to 180 ℃, remove unreacted diethylenetriamine and tetraethylene pentamine by underpressure distillation, promptly obtain diethylenetriamine-tetraethylene pentamine-Resins, epoxy E-51 end amido midbody solution, in the described end amido midbody solution, diethylenetriamine-tetraethylene pentamine-Resins, epoxy E-51 end amido intermediate is 0.25 mole.
(2) preparation of epoxy resin roughening and curing agent
With step (1) diethylenetriamine-tetraethylene pentamine that obtained-Resins, epoxy E-51 end amido midbody solution and 0.5 mole of epoxyoleic acid ethyl ester is that raw material is (excessive as end amido midbody solution viscosity, can add the diethylene glycol monomethyl ether solvent makes viscosity meet the stirring requirement), the temperature of question response diethylenetriamine-tetraethylene pentamine that container is adorned-Resins, epoxy E-51 end amido midbody solution is reduced to 65 ℃, under agitation 0.5 mole of epoxyoleic acid methyl esters is at the uniform velocity splashed into reaction vessel, the dropping time is 4 hours, after the epoxyoleic acid methyl esters is splashed into reaction vessel fully, under agitation continue reaction 2 hours in 65 ℃, reaction is reduced to room temperature after finishing, with the reaction product standing demix, separate the lower floor's product that obtains and be epoxy resin roughening and curing agent (color is lurid transparent liquid).Its general structure is as described in the summary of the invention part, contains R and is-C
2H
5, n be 1 and R be-C
2H
5, n is the epoxy resin roughening and curing agent of 3 two kinds of structural formula correspondences.
Embodiment 7
With the roughening and curing agent of traditional solidifying agent (prepolymer of polyamines and Resins, epoxy), present patent application embodiment 1 and embodiment 6 preparations is that metering in 1: 1 is got the raw materials ready by the mol ratio of epoxy resin E-44 and each solidifying agent respectively, and epoxy resin E-44 mixed with each solidifying agent respectively, then the above-mentioned three kinds epoxy resin E-44s that add different solidifying agent were solidified 8 hours at 50 ℃, again in 130 ℃ solidify 2 hours standby.
With the shock resistance of three kinds of Resins, epoxy after the above-mentioned curing by standard GB/T 1843-1996 preparation and specimen, the gained data see Table 1, use impact fracture face scanning electron microscope (SEM) photo of traditional solidifying agent (prepolymer of polyamines and Resins, epoxy) solidified epoxy resin E-44 to see Fig. 3, use impact fracture face scanning electron microscope (SEM) photo of the prepared roughening and curing agent solidified epoxy resin E-44 of present patent application embodiment 1 to see Fig. 4, use impact fracture face scanning electron microscope (SEM) photo of the prepared roughening and curing agent solidified epoxy resin E-44 of present patent application embodiment 6 to see Fig. 5.
Three kinds of epoxy resin E-44s after the above-mentioned curing are made sample carry out thermogravimetic analysis (TGA), test result sees Table 1.
The different solidifying agent solidified of table 1. epoxy resin E-44 mechanical property and thermal characteristics are relatively
From the data of table 1 as can be seen, roughening and curing agent of the present invention is compared with traditional solidifying agent, can significantly improve the shock strength of the Resins, epoxy after the curing, but thermal characteristics does not descend along with the raising of shock strength.
Claims (9)
1, a kind of epoxy resin roughening and curing agent is characterized in that its structural formula is as follows:
In the said structure formula, R is-CH
3,-C
2H
5, ,-C
4H
9,-C
8H
17In a kind of, n is 1 or 2 or 3.
2, a kind of preparation method of epoxy resin roughening and curing agent is characterized in that processing step is as follows:
(1) preparation of end amido intermediate
Containing at least 5 reactive amines with per molecule, to belong to the representative examples of saturated aliphatic polyamine of hydrogen atom and epoxy functionalities be that 2 Resins, epoxy is raw material, and the mol ratio of described representative examples of saturated aliphatic polyamine and described Resins, epoxy is 2: 1～4: 1;
In reaction vessel and another container, be respectively charged into a kind of solvent, described representative examples of saturated aliphatic polyamine is put into reaction vessel form representative examples of saturated aliphatic polyamine solution, described Resins, epoxy is put into another container form epoxy resin solution, the amount of solvent is exceeded with the requirement that the viscosity of formed solution meets stirring;
Representative examples of saturated aliphatic polyamine solution is heated to 50 ℃～80 ℃, under agitation epoxy resin solution is splashed into reaction vessel then, after epoxy resin solution is splashed into reaction vessel fully, under agitation continued polyreaction 2.5 hours～5.5 hours in 50 ℃～80 ℃, after reaction finishes, remove unreacted representative examples of saturated aliphatic polyamine by underpressure distillation, promptly obtain end amido midbody solution;
(2) preparation of epoxy resin roughening and curing agent
End amido midbody solution and Epoxy oil acid esters with step (1) preparation are raw material, and the mol ratio of end amido intermediate and Epoxy oil acid esters is 1: 2;
When the temperature that the question response container is adorned end amido midbody solution is 50 ℃～80 ℃, under agitation the Epoxy oil acid esters is splashed into reaction vessel, after the Epoxy oil acid esters is splashed into reaction vessel fully, under agitation continued polyreaction 2 hours～4 hours in 50 ℃～80 ℃, reaction is reduced to room temperature after finishing, with the reaction product standing demix, separate the lower floor's product that obtains and be epoxy resin roughening and curing agent.
3, the preparation method of epoxy resin roughening and curing agent according to claim 2 is characterized in that under protection of inert gas described representative examples of saturated aliphatic polyamine being put into reaction vessel forms representative examples of saturated aliphatic polyamine solution.
4,, it is characterized in that in the preparation process of described end amido intermediate that the dropping time of epoxy resin solution is 1.5 hours～2.5 hours according to the preparation method of claim 2 or 3 described epoxy resin roughening and curing agents; In the preparation process of described epoxy resin roughening and curing agent, the dropping time of Epoxy oil acid esters is 2 hours～4 hours.
5,, it is characterized in that described representative examples of saturated aliphatic polyamine is at least a in two inferior ethene triamines, Sanya ethene tetramine, four inferior ethene five amine according to the preparation method of claim 2 or 3 described epoxy resin roughening and curing agents.
6, the preparation method of epoxy resin roughening and curing agent according to claim 4 is characterized in that described representative examples of saturated aliphatic polyamine is at least a in two inferior ethene triamines, Sanya ethene tetramine, four inferior ethene five amine.
7,, it is characterized in that the Epoxy oil acid esters is a kind of in epoxyoleic acid methyl esters, epoxyoleic acid ethyl ester, epoxyoleic acid butyl ester, the epoxyoleic acid monooctyl ester according to the preparation method of claim 2 or 3 described epoxy resin roughening and curing agents.
8, the preparation method of epoxy resin roughening and curing agent according to claim 6 is characterized in that the Epoxy oil acid esters is a kind of in epoxyoleic acid methyl esters, epoxyoleic acid ethyl ester, epoxyoleic acid butyl ester, the epoxyoleic acid monooctyl ester.
9, according to the preparation method of claim 2 or 3 described epoxy resin roughening and curing agents, it is characterized in that described solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol list propyl ether, a kind of in the dipropylene glycol monobutyl ether.
The preparation method of 10 epoxy resin roughening and curing agents according to claim 8, it is characterized in that described solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol list propyl ether, a kind of in the dipropylene glycol monobutyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910167811A CN101659741A (en) | 2009-09-29 | 2009-09-29 | Epoxy resin toughening curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910167811A CN101659741A (en) | 2009-09-29 | 2009-09-29 | Epoxy resin toughening curing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101659741A true CN101659741A (en) | 2010-03-03 |
Family
ID=41788004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910167811A Pending CN101659741A (en) | 2009-09-29 | 2009-09-29 | Epoxy resin toughening curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101659741A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348490A (en) * | 2015-12-16 | 2016-02-24 | 太仓康盛化工有限公司 | Epoxy resin flexible curing agent |
| CN114230474A (en) * | 2021-12-10 | 2022-03-25 | 武汉市科达云石护理材料有限公司 | Epoxy resin toughening agent and preparation method thereof |
| CN116987365A (en) * | 2023-05-19 | 2023-11-03 | 广州聚佳新材料科技有限公司 | Low-temperature-resistant resin material and preparation process thereof |
-
2009
- 2009-09-29 CN CN200910167811A patent/CN101659741A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348490A (en) * | 2015-12-16 | 2016-02-24 | 太仓康盛化工有限公司 | Epoxy resin flexible curing agent |
| CN114230474A (en) * | 2021-12-10 | 2022-03-25 | 武汉市科达云石护理材料有限公司 | Epoxy resin toughening agent and preparation method thereof |
| CN114230474B (en) * | 2021-12-10 | 2024-04-02 | 武汉市科达云石护理材料有限公司 | Epoxy resin toughening agent and preparation method thereof |
| CN116987365A (en) * | 2023-05-19 | 2023-11-03 | 广州聚佳新材料科技有限公司 | Low-temperature-resistant resin material and preparation process thereof |
| CN116987365B (en) * | 2023-05-19 | 2024-04-30 | 广州聚佳新材料科技有限公司 | Low-temperature-resistant resin material and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gerbase et al. | Dynamic mechanical and thermal behavior of epoxy resins based on soybean oil | |
| EP1865013B1 (en) | Polyamide curing agent compositions | |
| CN101555386B (en) | Epoxy organosilicone ultraviolet curing coating modified by (methyl) acrylic acid and preparation method thereof | |
| US10392468B2 (en) | Highly functional natural material-derived epoxy resin, preparation method therefor, and epoxy resin curing composition using same | |
| CN1747985A (en) | Silicon compound containing epoxy group and thermosetting resin composition | |
| US20070287808A1 (en) | Polyamide curing agent compositions | |
| CN113583216B (en) | Bio-based epoxy resin containing silicon-oxygen bond and preparation and application methods thereof | |
| CN105482713A (en) | Highly-disproportionated rosin glycidyl methacrylate and preparation method thereof | |
| US7655736B2 (en) | Polyamide curative from substituted amine mixture and dimer fatty acid or ester | |
| CN109384775A (en) | A kind of biological base epoxy presoma and its preparation method and application containing cyclic amide structure | |
| US8481622B2 (en) | Soybean based epoxy resin and methods of making and use | |
| CN111040131A (en) | Synthesis and application of epoxy resin based on catechin | |
| CN106750528A (en) | A kind of phosphorus azepine ring structure fire retarding epoxide resin and its synthetic method | |
| JP2014173088A (en) | Epoxy resin-added matter and thermosetting resin of the same | |
| CN101280056A (en) | Method for preparing C21dicarboxylic acid polyamide epoxy hardener from methyl eleostearate | |
| CN103588976A (en) | Synthesis method of unsaturated hyperbranched polyamides | |
| KR20010086434A (en) | Highly branched oligomers, process for their preparation and applications thereof | |
| CN101659741A (en) | Epoxy resin toughening curing agent and preparation method thereof | |
| CN111303435A (en) | Tung oil-based nonionic self-emulsifying waterborne epoxy curing agent and preparation method thereof | |
| KR101848704B1 (en) | Branch-type amine-based epoxy resin curing agent, and method of manufacturing the same, and epoxy resin composition using the same | |
| CN109777040A (en) | A kind of biomass-based recoverable version epoxy resin and its preparation method and application | |
| CN108794984A (en) | A kind of residual heavy modified epoxy and its preparation method and application of impact resistance high fever | |
| CN112759565B (en) | Grease-based polyamine curing agent and preparation method and application thereof | |
| JPS6348325A (en) | Bridging agent made from amino fatty acid amide | |
| CN105153407B (en) | A kind of thermosetting rosin resin compositions and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100303 |