CN104086750B - Application of curing agent 1,2-bi(2,6-dioxo-4-morpholinyl) ethane in epoxy resin system - Google Patents
Application of curing agent 1,2-bi(2,6-dioxo-4-morpholinyl) ethane in epoxy resin system Download PDFInfo
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Abstract
The invention discloses an application method of 1,2-bi(2,6-dioxo-4-morpholinyl) ethane (EDTAD) as a novel curing agent in an epoxy resin system. The method comprises the following steps: heating epoxy resin to 80 DEG C in advance, and then adding 1,2-bi(2,6-dioxo-4-morpholinyl) ethane; optionally adding an accelerant and/or a filler, evenly stirring and mixing the raw materials to mold, and then curing the obtained resin mixture. The volume shrinkage rate of the epoxy resin and the composite material thereof in the curing process is reduced by the application of the novel epoxy resin expanding curing agent 1,2-bi(2,6-dioxo-4-morpholinyl) ethane, and the volume shrinkage rate of the epoxy resin system is reduced to 0-0.5%.
Description
Technical field
The present invention relates to a kind of double (2,6- dioxy -4- morpholinyls) ethane of Novel curing agent 1,2- are in epoxy-resin systems
Using.
Background technology
There is certain volume contraction in the curing process in thermosetting resin.Such as wide variety of epoxy resin, it solidified
Cubical contraction is generally higher than 5% in journey.Volume contraction has a great impact for the performance of thermosetting resin.Epoxy resin is consolidated
Because volume contraction is inevitably generated residual stress during change, stress concentration can cause material internal defect to cause, such as slight crack
With lattice defect etc..Therefore, the shrinkage stress of material is the problem that can not be ignored, and it is a potential destructive factor so that
Inside resin matrix, between gluded joint (adhesive) or resin matrix and fiber interface (composite) without outer active force just
There is certain stress, cause the degumming of gluded joint, the decline of resin matrix intensity, the cracking of composite and size shakiness
It is fixed etc., so as to affect composite service life.It is improve thermosetting resin performance one to weaken and even eliminate volume contraction
Important indicator.
It is right to solve the problems, such as volume contraction during epoxy resin cure, Chinese scholars such as Bailey, Endo, Ortiz etc.
Expanding Monomer, such as spiro orthocarbonate class compound have done more research, obtain certain achievement, to a certain extent can be with
Reduce cubical contraction, but this kind of compound is limited only to the experimental stage, also has larger distance with practical application.
The content of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art, and provides Novel curing agent
1,2- double (2,6- dioxy -4- morpholinyls) ethane epoxy-resin systems application, to reduce epoxy resin and its composite
Cubical contraction in the curing process, epoxy-resin systems cubical contraction is reduced to 0～0.5%.
The present invention is to solve the problems, such as that adopted technical scheme set forth above is：
1,2- double (2,6- dioxy -4- morpholinyls) ethane, its molecular formula is C10N2O6H12, structural formula is
Double (2,6- dioxy -4- morpholinyls) ethane (EDTAD) of 1,2- answering in epoxy-resin systems as Novel curing agent
With.Using when, according to the actual requirements, by appropriate curing agent 1, double (2, the 6- dioxy -4- morpholinyls) ethane (EDTAD) of 2- are added
It is well mixed in epoxy-resin systems, and Jing after shaping, solidification, solidify afterwards, epoxy-resin systems are in whole solidification process
Shrinkage factor can be reduced to 0～0.5%.
Double (2,6- dioxy -4- morpholinyls) ethane (EDTAD) the answering in epoxy-resin systems of above-mentioned Novel curing agent 1,2-
With method, comprise the following steps：
(1) it is the 30%～60% of epoxy resin quality according to double (2,6- dioxy -4- morpholinyls) the ethane consumptions of 1,2-, will
After epoxy resin is heated in advance 80 DEG C, add double (2, the 6- dioxy -4- morpholinyls) ethane of 1,2-, be uniformly mixed and into
Type, by gained resin compound 100 DEG C of 2～4h of solidification are heated to, and are continuously heating to 140～150 DEG C of 13～18h of solidification, are obtained
Epoxy resin-cured product；
(2) solidify afterwards：By step (1) products therefrom prior to 150～160 DEG C of 2～3h of solidification, 170～200 are then heated to
DEG C 3～5h of resolidification, epoxy-resin systems cubical contraction in the curing process is reduced to 0～0.5%.
Double (2,6- dioxy -4- morpholinyls) ethane (EDTAD) of above-mentioned Novel curing agent 1,2- are in the another of epoxy-resin systems
A kind of application process, comprises the following steps：
On the basis of the quality of epoxy resin, according to curing agent 1, the consumption of double (2, the 6- dioxy -4- morpholinyls) ethane of 2-
It is the 40～60% of epoxy resin quality, by curing agent 1, double (2, the 6- dioxy -4- morpholinyls) ethane of 2- and epoxy resin mix
After uniform, filler is added, be uniformly mixed and be molded, gained resin compound is heated to into 100 DEG C of 2～4h of solidification, continued
150～160 DEG C of 13～18h of solidification are warming up to, continue to be warmed up to 160～170 DEG C of 2～4h of solidification, 10 are then solidified at room temperature
～15h, in the curing process shrinkage factor is reduced to 0～0.5% to epoxy-resin systems.
Double (2,6- dioxy -4- morpholinyls) ethane (EDTAD) of above-mentioned Novel curing agent 1,2- in epoxy-resin systems the
Three kinds of application processes, comprise the following steps：
It is the 0.3～3% of epoxy resin quality according to the consumption of accelerator on the basis of the quality of epoxy resin, solidification
Agent 1, the consumption of double (2, the 6- dioxy -4- morpholinyls) ethane of 2- is the 40～60% of epoxy resin quality, and by curing agent 1,2- is double
After (2,6- dioxy -4- morpholinyls) ethane and epoxy resin are well mixed, accelerator is added, be uniformly mixed and be molded, will
Gained resin compound is heated to 100 DEG C of 2～4h of solidification, and 8～12h is solidified at 120 DEG C, and products therefrom is solid prior to 130-140 DEG C
Change 3～4h, 10～15h is then solidified at room temperature, in the curing process shrinkage factor is reduced to 0～0.5% to epoxy-resin systems.
By such scheme, it is described be shaped in the method such as compression molding, moulding by casting, hand pasting forming, Wrapping formed appoint
Meaning is a kind of.
By such scheme, described epoxy resin is E-54, E-51, E-44, the asphalt mixtures modified by epoxy resin such as E-42, CYD127, CYD128
One or more in fat mixture in any proportion.
By such scheme, the accelerator is that triethylene diamine, TEPA, polyethylene polyamine, DMP-30 etc. promote
One or more in agent mixture in any proportion.
By such scheme, described filler be precipitated calcium carbonate, diatomite, talcum powder etc. it is therein one or more by any
The mixture of ratio, amount of filler is the 2～4% of epoxy resin mass fraction.
Double (2,6- dioxy -4- morpholinyls) ethane of Novel curing agent 1,2- are applied to consolidating for epoxy-resin systems in the present invention
Change mechanism as shown in Figure 1.Under conditions of without accelerator, 1,2- double (2,6- dioxy -4- morpholinyls) ethane first with resin in
The carboxyl reaction dissociated in hydroxyl or acid anhydrides, generates monoesters, and the monoesters of generation or hydroxyl continue and epoxy reaction, ultimately produce
Space network, this reaction is acid anhydrides ring-opening polymerization.There are two C-O singly-bounds fractures to become C=O in this course of reaction
Double bond, this is the process that a Van der Waals distance is changed into covalent distance, can cause volume contraction；Meanwhile, acid anhydrides ring-opening reaction
The singly-bound fracture of middle C-O can be transformed into close intermolecular model ylid bloom action moment from so as to cause volumetric expansion.Due to covalent
The close Van der Waals distance of volumetric expansion that distance is changed into Van der Waals distance and causes is changed into the contraction that covalent distance causes, just
Reduce the volume contraction for even offsetting curing system to a certain extent.When with the presence of Tertiary amine accelerators, tertiary amine casts the first stone acid
Acid anhydride, generates stable carboanion, and carboanion and the epoxy reaction of generation generate alcoxyl anion, alcoxyl anion
Continue anhydride reaction, generate carboanion, so repeatedly, ultimately produce space network.
Compared with prior art, this invention beneficial effect is：
The present invention is by a kind of double (2,6- dioxy -4- morpholinyls) ethane of new epoxy expansion curing agent 1,2-
Using, to reduce epoxy resin and its composite cubical contraction in the curing process, the epoxy-resin systems volume
Shrinkage factor is reduced to 0～0.5%, and this kind of expansible curing agent can be applied to adhering with epoxy resin, embedding；Glass fibers
The techniques such as winding, molding, the injection of dimension reinforced resin based composites, its using value and economic worth are projected.
Description of the drawings
Fig. 1 is the curing mechanism that double (2,6- dioxy -4- morpholinyls) ethane of 1,2- are applied to epoxy-resin systems.
Fig. 2 is the product infrared spectrogram in embodiment 1 Jing after solidify afterwards.
Specific embodiment
For a better understanding of the present invention, present disclosure is further elucidated with reference to example, but the present invention is not only
It is limited only to the following examples.
Novel curing agent of the present invention 1, the preparation method of double (2, the 6- dioxy -4- morpholinyls) ethane of 2-, detailed process
It is as follows：
1) it is 1 according to mol ratio by EDTA and acetic anhydride：10 are added in single necked round bottom flask, and flask top installs one
Ball-type condenser with drying tube, is passed through inert gas, opens magnetic agitation, in 80 DEG C of water bath with thermostatic control 24-30h, stops adding
Heat and stirring, are cooled to room temperature, remove upper liquid and suction filtration, obtain double (2, the 6- dioxy -4- morpholinyls) ethane (EDTAD) of 1,2-
Crude product；
2) crude product is dissolved in the conical flask with ground equipped with acetic anhydride, covers bottle stopper, carry out intermittent oscillation, half
Hour carries out suction filtration, and repeat the above steps are finally washed with a small amount of ether, drained, and is put into drying box drying, obtains 1,2- double
(2,6- dioxy -4- morpholinyls) ethane, yield is 80%.
The equation of above-mentioned reaction is as follows：
Embodiment 1
Novel curing agent 1, in the application process of epoxy-resin systems, it is walked double (2, the 6- dioxy -4- morpholinyls) ethane of 2-
It is rapid as follows：
(1) according to the mass fraction, double (2, the 6- dioxy -4- morpholinyls) ethane 45 of 100 parts of E-51 epoxy resin, 1,2- are weighed
Part, epoxy resin is preheated to 80 DEG C, double (2, the 6- dioxy -4- morpholinyls) ethane of 1,2- are added, it is uniformly mixed, cast,
Bubble is excluded, gained resin compound is heated to into 100 DEG C of solidification 3h, be continuously heating to 145 DEG C of solidification 15h, obtain asphalt mixtures modified by epoxy resin
Fat solidfied material；
(2) solidify afterwards：By step (1) products therefrom prior to 155 DEG C of 2～3h of solidification, solidify at being then warming up to 185 DEG C
5h, E-51 epoxy resin shrinkage factor in whole solidification process is reduced to 0～0.5%.
Using the Volume Changes of dilatometer tracking measurement epoxy resin solidifying system, determine epoxy resin and entirely solidifying
Cubical contraction in journey is 0.4%.
Fig. 2 is that the epoxy resin cured product of double (2,6- dioxy -4- morpholinyls) ethane of 1,2- carries out the infrared light of solidify afterwards
Spectrogram.As can be seen from Figure 2,1690.18cm-1For the stretching vibration of C=O, 1,2- double (2,6- dioxy -4- morpholinyls) ethane
1808cm-1、1762cm-1Two acid anhydrides absworption peaks disappear, 1244.77cm-1And 1046.53cm-1For the C-O of carboxylate, thus
There is ring-opening reaction in double (2, the 6- dioxy -4- morpholinyls) ethane of provable 1,2-, generate carboxylate in cured epoxy resin process.
Embodiment 2
Novel curing agent 1, in the application process of epoxy-resin systems, it is walked double (2, the 6- dioxy -4- morpholinyls) ethane of 2-
It is rapid as follows：
(1) according to the mass fraction, 100 parts of epoxy resin E-44s, curing agent 1 are weighed, 2- is double (2,6- dioxy -4- morpholinyls)
40 parts of ethane, 0.3 part of altax P-30, epoxy resin is preheated to 80 DEG C, adds double (2, the 6- dioxy -4- morpholines of 1,2-
Base) ethane and DMP-30, after being well mixed, with glass fiber dipped Wrapping formed, gained resin compound is heated to into 100 DEG C
Solidification 4h, at 120 DEG C 12h is solidified；
(2) solidify afterwards：By step (1) products therefrom prior to 135 DEG C of solidification 4h, 12h, asphalt mixtures modified by epoxy resin are then solidified at room temperature
Cubical contraction of the fat in whole solidification process is less than 0.4%.
, embodiment 3
Novel curing agent 1, in the application process of epoxy-resin systems, it is walked double (2, the 6- dioxy -4- morpholinyls) ethane of 2-
It is rapid as follows：
(1) according to the mass fraction, 100 parts of E-54 epoxy resin, curing agent 1 are weighed, 2- is double (2,6- dioxy -4- morpholinyls)
45 parts of ethane, 0.3 part of altax P-30, epoxy resin is preheated to 80 DEG C, adds curing agent and accelerator, stirring mixing
After uniform, bubble, glass fiber reinforcement injection moulding are excluded, gained resin compound is heated to into 100 DEG C of solidification 2h, 120 DEG C
Solidification 15h；
(2) solidify afterwards：By step (1) products therefrom prior to 130 DEG C of solidification 4h, 15h, asphalt mixtures modified by epoxy resin are then solidified at room temperature
Cubical contraction of the fat in whole solidification process is less than 0.5%.
Embodiment 4
Novel curing agent 1, in the application process of epoxy-resin systems, it is walked double (2, the 6- dioxy -4- morpholinyls) ethane of 2-
It is rapid as follows：
(1) according to the mass fraction, curing agent 1,2- double (2,6- dioxy -4- morpholinyls) 50 parts of ethane, filler lightweights are weighed
3 parts of calcium carbonate is added in 100 parts of E-51 epoxy resin, and resin compound is preheated to into 80 DEG C, is uniformly mixed, and excludes gas
Gained resin compound is heated to 100 DEG C of solidification 4h by bubble, glass fibre pultrusion, is continuously heating to 160 DEG C of solidification 18h；
(2) solidify afterwards：By step (1) products therefrom prior to 160 DEG C of solidification 2h, continuation solidifies at room temperature 10h, E-51 rings
Cubical contraction of the oxygen tree fat in whole solidification process is less than 0.5%.
Certainly, in Novel curing agent 1, when double (2, the 6- dioxy -4- morpholinyls) ethane of 2- are applied to epoxy-resin systems, promote
Enter agent and filler can be while add, the time and temperature of addition and follow-up curing reaction slightly adjust.
The above is only the preferred embodiment of the present invention, it is noted that for one of ordinary skill in the art comes
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (8)
- Double (2,6- dioxy -4- morpholinyls) ethane of 1.1,2- as curing agent epoxy-resin systems application.
- 2. double (2,6- dioxy -4- morpholinyls) ethane of curing agent 1,2- according to claim 1 are in epoxy-resin systems Application process, it is characterised in that comprise the following steps：(1) it is the 30%～60% of epoxy resin quality according to double (2,6- dioxy -4- morpholinyls) the ethane consumptions of 1,2-, by epoxy After resin is previously heated to 80 DEG C, double (2, the 6- dioxy -4- morpholinyls) ethane of 1,2- are added, be uniformly mixed, by gained tree Lipoprotein mixture is heated to 100 DEG C of 2～4h of solidification, is continuously heating to 140～150 DEG C of 13～18h of solidification, obtains molding for epoxy resin Solidfied material；(2) solidify afterwards：By step (1) products therefrom prior to 150～160 DEG C of 2～3h of solidification, 170～200 DEG C are then heated to admittedly Change 3～5h, epoxy resin cubical contraction in the curing process is reduced to 0～0.5%.
- 3. double (2,6- dioxy -4- morpholinyls) ethane of curing agent 1,2- according to claim 1 are in epoxy-resin systems Application process, it is characterised in that comprise the following steps：On the basis of the quality of epoxy resin, according to curing agent 1, the consumption of double (2, the 6- dioxy -4- morpholinyls) ethane of 2- is ring The 40～60% of oxygen resin quality, by curing agent 1, double (2, the 6- dioxy -4- morpholinyls) ethane of 2- and epoxy resin are well mixed Afterwards, filler is added, is uniformly mixed, gained resin compound is heated to into 100 DEG C of 2～4h of solidification, it is continuously heating to 150～ 160 DEG C of solidification 13～18h shapings, continue to be warmed up to 160～170 DEG C of 2～4h of solidification, and 10～15h, ring are then solidified at room temperature Oxygen tree fat cubical contraction in the curing process is less than 0.5%.
- 4. double (2,6- dioxy -4- morpholinyls) ethane of curing agent 1,2- according to claim 3 are in epoxy-resin systems Application process, it is characterised in that described filler be precipitated calcium carbonate, diatomite, talcum powder in one or more in any proportion Mixture, amount of filler for epoxy resin mass fraction 2～4%.
- 5. double (2,6- dioxy -4- morpholinyls) ethane of curing agent 1,2- according to claim 1 are in epoxy-resin systems Application process, it is characterised in that comprise the following steps：It is the 0.3～3% of epoxy resin quality according to the consumption of accelerator on the basis of the quality of epoxy resin, curing agent 1, The consumption of double (2, the 6- dioxy -4- morpholinyls) ethane of 2- is the 40～60% of epoxy resin quality, by curing agent 1,2- double (2,6- Dioxy -4- morpholinyls) after ethane and epoxy resin is well mixed, accelerator is added, it is uniformly mixed, by gained mixed with resin Thing is heated to 100 DEG C of 2～4h of solidification, and 8～12h shapings are solidified at 120 DEG C, solidifies 3～4h at 130～140 DEG C then, then exists Room temperature condition solidifies 10-15h, and in the curing process shrinkage factor is reduced to 0～0.5% to epoxy resin.
- 6. double (2,6- dioxy -4- morpholinyls) ethane of curing agent 1,2- according to claim 5 are in epoxy-resin systems Application process, it is characterised in that the accelerator is in triethylene diamine, TEPA, polyethylene polyamine, DMP-30 Plant or several mixtures in any proportion.
- 7. double (2,6- dioxy -4- morpholinyls) ethane of curing agent 1,2- according to one of claim 2-4 are in epoxy resin The application process of system, it is characterised in that it is described be shaped to compression molding, moulding by casting, hand pasting forming, it is Wrapping formed in appoint Meaning is a kind of.
- 8. double (2,6- dioxy -4- morpholinyls) ethane of curing agent 1,2- according to one of claim 2-4 are in epoxy resin The application process of system, it is characterised in that described epoxy resin is E-54, E-51, E-44, in E-42, CYD127, CYD128 One or more mixtures in any proportion.
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