CN104945600B - A kind of epoxy curing agent of the benzoxazine of list containing aliphatic cyclic amine type and preparation method thereof - Google Patents
A kind of epoxy curing agent of the benzoxazine of list containing aliphatic cyclic amine type and preparation method thereof Download PDFInfo
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- CN104945600B CN104945600B CN201510426681.2A CN201510426681A CN104945600B CN 104945600 B CN104945600 B CN 104945600B CN 201510426681 A CN201510426681 A CN 201510426681A CN 104945600 B CN104945600 B CN 104945600B
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- curing agent
- epoxy resin
- benzoxazine
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- aliphatic cyclic
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Abstract
The invention discloses a kind of epoxy curing agent of the benzoxazine of list containing aliphatic cyclic amine type and preparation method thereof, the structural formula of wherein curing agent is：
Description
First, technical field
The present invention relates to a kind of curing agent and preparation method thereof, specifically a kind of ring of the benzoxazine of list containing aliphatic cyclic amine type
Oxygen resin curing agent and preparation method thereof, is used as the high-grade curing agent of epoxy resin.
2nd, background technology
Epoxy resin has the title of all-purpose adhesive, with good mechanical property, adhesive property, electrical insulating property, chemical stability
And processability, extensive use and the field such as building, machinery, electronic apparatus, space flight and aviation.Epoxy resin is with curing agent certain
Under the conditions of solidify crosslinking, form three-dimensional netted three-dimensional-structure, therefore in the application and development of epoxy resin, curing agent has
Very important effect.
Methyl ring pentanediamine (TAC) has the five-membered ring structure of saturation, as the curing agent of epoxy resin, has and polyethers
The similar space conformation of amine structure is more, the good feature of compliance, while having the rigidity and intensity of aromatic amine cyclic structure again, with ring
The cured product good mechanical performance of oxygen tree fat, colourity and gloss are better than fatty amine and polyamide, pass through rational structure design
It is expected to bond strength and toughness.Close to cyclohexanediamine and IPD in the structure of methyl ring pentanediamine, and valency
Lattice are but far below such product, and raw material, based on the country, its potential advantages is fairly obvious, can consolidate as a kind of new
Agent is used.At present, it is less on the foundation structure of cycloaliphatic amines curing agent and the research report of performance, but have extensively in future
Wealthy application prospect.
Benzoxazine colophony is a kind of novel hot setting phenolic resin grown up on the basis of traditional phenolic resin,
Typically be synthesized into by phenol, amine and paraformaldehyde, be the hexa-member heterocycle system that oxygen, nitrogen-atoms are constituted, be initially by Holly and
Cope has found in research Mannich reactions.Benzoxazine colophony not only has the advantages that traditional phenolic resin, also with synthesis
Technique is simple, wide material sources, with low cost, and curing reaction is not required to catalyst and released without small molecule, and the voidage of product is low several
The excellent properties such as ungauged regions.Therefore, benzoxazine colophony prepare it is significant, in works such as Aero-Space, electronics, automobiles
The application in industry field is paid attention to by more and more extensive, has broad application prospects.
3rd, the content of the invention
The present invention is intended to provide a kind of epoxy curing agent of the benzoxazine of list containing aliphatic cyclic amine type and preparation method thereof, institute
The problem of solving is by controlling its charge ratio methyl ring pentanediamine is retained an amine and synthesize the spy of single benzoxazine ring
Different curing agent structure, the significant heat endurance improved with epoxy resin cured product.
The present invention obtains new curing agent by using nonyl phenol, modified formaldehyde TAC, reduces the volatility of low-grade amine,
Excitant and toxicity, low-viscosity (mobile) liquid are easily mixed with epoxy resin, wide with epoxy resin ratio range, are adjustably controlled solid
Change speed.
The present invention obtains new curing agent by using nonyl phenol, modified formaldehyde TAC, applies the invention to epoxy resin
System also improves solidfied material in addition to retaining epoxy resin good cementability, chemical stability, electrical insulating property and processability
The advantages of heat endurance, pliability.
The structural formula of the epoxy curing agent of the benzoxazine type of list containing aliphatic cyclic amine of the invention is as follows：
The preparation method of the epoxy curing agent of the benzoxazine type of list containing aliphatic cyclic amine of the invention comprises the following steps：
At ambient temperature, 0.05mol TAC and 0.1mol paraformaldehydes are added into reactor, are then added under agitation
Enter 30ml organic solvents, 0.05mol nonyl phenols are added after being well mixed, be warming up to 85 DEG C and react 5 hours, rotary evaporation removes molten
Target product is produced after agent and water, vacuum drying, is gluey liquid.
Course of reaction is as follows：
The organic solvent is selected from absolute ethyl alcohol, dioxane or toluene.
The process of the curing agent cured epoxy resin prepared with the present invention is as follows：
By epoxy resin (E44) and curing agent of the present invention according to 1：0.6 mass ratio mixing, stands after stirring and displays
To remove the gas being mixed into during stirring, epoxy resin cured product is obtained after solidification.Curing process is as follows：
Blend composition is placed in ceramic crucible, then ceramic crucible is placed in air dry oven, 100 DEG C are warming up to successively
1h, 120 DEG C of insulation 1h, 150 DEG C of insulation 2h, 180 DEG C of insulation 2h, 200 DEG C of insulation 2h, 210 DEG C of insulation 1h are incubated, asphalt mixtures modified by epoxy resin is obtained
Fat solidfied material.
The advantage of both aliphatic cyclic amine and benzoxazine is combined by curing agent of the present invention, while nonyl phenol (NP) odorless, nothing
Malicious, nonirritant, price is low, and can also solidify under low temperature, moist environment, and nonyl phenol has-C9H19Long link
Structure, so as to dramatically increase the pliability of pouring piece.
At present, the curing agent structure of methyl ring pentanediamine and benzoxazine being combined not yet is reported at home at present.
Curing agent structure of the present invention especially, contains-NH simultaneously2- and benzoxazine structure, it can solidify in room temperature,
But benzoxazine structure then need at high operating temperatures could open loop generation phenolic hydroxyl group and epoxy resin further solidify crosslinking,
Cold curing is not fully cured.
Compared with the prior art, beneficial effects of the present invention are embodied in：
1st, benzoxazine is successfully introduced into curing agent by curing agent of the present invention, assigns the thermal stability of epoxy resin.
2nd, the C containing nonyl phenol in curing agent of the present invention9H19Long-chain, assign the good pliability of epoxy resin cured product
Energy.
3rd, the preparation technology of curing agent of the present invention is simple, and solvent can be with multiple choices, it is easy to accomplish industrialized production, cost
Cheap, yield is more than 80%.
4th, illustrate
Fig. 1 is methyl ring pentanediamine (curve a) and curing agent of the present invention (curve b) infrared comparative analysis figure.The present invention
Curing agent in 935cm-1Occur in that in the characteristic absorption peak for the phenyl ring being connected Yu oxazine ring, curve a do not there is this peak；
1390cm-1The C-N stretching vibration absworption peaks of Zuo You Wei oxazine rings；The symmetric and anti-symmetric stretching vibration of Ar-O-C in oxazine ring
Absworption peak appears in 1060cm-1And 1250cm-1Place；1500cm-1And 1600cm-1Place is the feature of trisubstituted benzene ring stretching vibration
Absworption peak；In 3300cm-1Left and right occurs in that-NH2Primary amine salt characteristic peak.In summary, target product has been obtained.
Fig. 2 is curing agent of the present invention1H-NMR spectrum, with CDCl3For solvent, peak δ=7.2 are the proton peak of solvent, figure
Middle peak δ=4.0 represent the-O-CH in benzoxazine2- N- hydrogen b proton peak, the expression-CH of peak δ=4.922- hydrogen a proton peak,
Peak δ=2.7 represent the connected-CH of alicyclic ring2- hydrogen c proton peak, peak δ=3.7 represent aliphatic cyclic amine-NH2Hydrogen Proton peak, peak δ=
6.72-7.1 represents the proton peak of Ar-H on phenyl ring, and peak δ=0.6-1.6 represents the-CH on five-membered ring2,-CH3Proton peak, knot
Closing infrared analysis confirms that synthesized sample is target product.
Fig. 3 is epoxy resin cured product (the curve a) and with methyl ring penta 2 obtained with curing agent hot setting of the present invention
Amine is epoxy resin cured product (curve b) the TG comparative analysis figures that curing agent hot setting is obtained.Figure it is seen that with
The epoxy resin cured product heat decomposition temperature that curing agent solidification of the present invention is obtained is 370 DEG C, using methyl ring pentanediamine as curing agent
It is 328 DEG C to solidify obtained epoxy resin cured product heat decomposition temperature, and heat decomposition temperature improves 42 DEG C, so that material is overall
Heat resistance have good raising and improvement.
Fig. 4 is to solidify obtained epoxy resin cured product (curve a) and with the present invention with curing agent hot conditions of the present invention
Epoxy resin cured product (curve b) the TG comparative analysis figures that the solidification of curing agent room temperature condition is obtained.From fig. 4, it can be seen that with
The epoxy resin cured product heat decomposition temperature that curing agent hot setting of the present invention is obtained is 370 DEG C, with curing agent room temperature of the present invention
It is 310 DEG C to solidify obtained epoxy resin cured product heat decomposition temperature, and heat decomposition temperature improves 60 DEG C, it can be seen that in high temperature
Under the conditions of solidification crosslinking it is more abundant so that the heat resistance of material is greatly improved.
5th, specific implementation method
With reference to embodiment, the present invention is described in detail, but the present invention does not limit to following examples.
Embodiment 1：
1st, the preparation of aliphatic cyclic amine list benzoxazine curing agent
At ambient temperature, into the 250mL three-necked flasks equipped with condenser pipe and stirring rod plus 12g methyl ring pentanediamines and
6g paraformaldehydes, add 20ml absolute ethyl alcohols and make solvent dissolving, wherein paraformaldehyde is added in three times, during the interval added every time
Between be 10 minutes；The nonylbenzene phenol that 22g is added after half an hour is stirred at room temperature, is warming up to 85 DEG C and reacts 5 hours, rotary evaporation removes molten
The epoxy curing agent of the benzoxazine type of list containing aliphatic cyclic amine, yield 80% are produced after agent and water, vacuum drying.Test its infrared
See Fig. 1 and Fig. 2 with nuclear magnetic data.
2nd, the solidification of epoxy resin
Curing agent prepared by epoxy resin E44 and step 1 is according to 1：0.6 quality is than batch mixing, and stirring makes it uniform, quiet
The gas displayed and be mixed into remove during stirring is put, blend composition is placed in ceramic crucible, ceramic crucible then is placed in into air blast does
In dry case, be warming up to successively 100 DEG C insulation 1h, 120 DEG C insulation 1h, 150 DEG C insulation 2h, 180 DEG C insulation 2h, 200 DEG C insulation 2h,
210 DEG C of insulation 1h, obtain epoxy resin cured product.
Contrast experiment --- curing agent cured epoxy resin is used as using methyl ring pentanediamine
By epoxy resin (E44) and raw material methyl ring pentanediamine according to 1:0.25 quality makes it uniform than batch mixing, stirring,
The gas displayed and be mixed into remove during stirring is stood, blend composition is placed in ceramic crucible, ceramic crucible is then placed in air blast
In drying box, 100 DEG C of insulation 1h, 120 DEG C of insulation 1h, 150 DEG C of insulation 2h, 180 DEG C of insulation 2h, 200 DEG C of insulations are warming up to successively
2h, 210 DEG C of insulation 1h, obtain epoxy resin cured product.
During solidification, the mass ratio between epoxy resin and TAC curing agent is 1:0.25, epoxy resin and curing agent of the present invention
Between mass ratio be 1:0.6, this ratio is calculated according to the equivalent value of epoxy resin.Curing agent/ring of the present invention
Oxygen resin cured matter and TAC/ epoxy resin cured products test TG such as Fig. 3.
Embodiment 2：
1st, the preparation of aliphatic cyclic amine list benzoxazine curing agent
At ambient temperature, into the 250mL three-necked flasks equipped with condenser pipe and stirring rod plus 12g methyl ring pentanediamines and
6g paraformaldehydes, add 20ml dioxane and make solvent dissolving, wherein paraformaldehyde is added in three times, during the interval added every time
Between be 10 minutes；The nonylbenzene phenol that 22g is added after half an hour is stirred at room temperature, is warming up to 85 DEG C and reacts 5 hours, rotary evaporation removes molten
The epoxy curing agent of the benzoxazine type of list containing aliphatic cyclic amine, yield 80% are produced after agent and water, vacuum drying.
2nd, the solidification of epoxy resin
Curing agent prepared by epoxy resin E44 and step 1 is according to 1：0.6 quality is than batch mixing, and stirring makes it uniform, quiet
The gas displayed and be mixed into remove during stirring is put, blend composition is placed in ceramic crucible, solidifies 7 days at room temperature, obtains epoxy
Resin cured matter.Its TG is tested, and is compared with the solidification TG of hot conditions, such as Fig. 4.
Embodiment 3：
1st, the preparation of aliphatic cyclic amine list benzoxazine curing agent
At ambient temperature, into the 250mL three-necked flasks equipped with condenser pipe and stirring rod plus 12g methyl ring pentanediamines and
6g paraformaldehydes, add 20ml toluene and make solvent dissolving, wherein paraformaldehyde is added in three times, and the interval time added every time is
10 minutes；Be stirred at room temperature after half an hour add 22g nonylbenzene phenol, be warming up to 85 DEG C react 5 hours, rotary evaporation remove solvent and
The epoxy curing agent of the benzoxazine type of list containing aliphatic cyclic amine, yield 80% are produced after water, vacuum drying.
2nd, the solidification of epoxy resin
Curing agent prepared by epoxy resin E44 and step 1 is according to 1：0.6 quality is than batch mixing, and stirring makes it uniform, quiet
The gas displayed and be mixed into remove during stirring is put, blend composition is placed in ceramic crucible, ceramic crucible then is placed in into air blast does
In dry case, be warming up to successively 100 DEG C insulation 1h, 120 DEG C insulation 1h, 150 DEG C insulation 2h, 180 DEG C insulation 2h, 200 DEG C insulation 2h,
210 DEG C of insulation 1h, obtain epoxy resin cured product.
Claims (3)
1. a kind of epoxy curing agent of the benzoxazine of list containing aliphatic cyclic amine type, it is characterised in that its structure is：
2. a kind of preparation method of the epoxy curing agent of the benzoxazine type of list containing aliphatic cyclic amine described in claim 1, it is special
Levy and be to comprise the following steps：
At ambient temperature, 0.05mol methyl ring pentanediamines and 0.1mol paraformaldehydes are added into reactor, under then stirring
30ml organic solvents are added, 0.05mol nonyl phenols are added after being well mixed, 85 DEG C is warming up to and reacts 5 hours, rotary evaporation is removed
Target product is produced after solvent and water, vacuum drying；
The organic solvent is selected from absolute ethyl alcohol, dioxane or toluene.
3. a kind of method of curing agent cured epoxy resin with described in claim 1, it is characterised in that comprise the following steps：
By epoxy resin and curing agent according to 1：0.6 mass ratio mixing, stands to display after stirring and is mixed with removing during stirring
The gas entered, epoxy resin cured product is obtained after solidification；
The technical process of the solidification is as follows：
Blend composition is placed in ceramic crucible, then ceramic crucible is placed in air dry oven, 100 DEG C of insulations are warming up to successively
1h, 120 DEG C of insulation 1h, 150 DEG C of insulation 2h, 180 DEG C of insulation 2h, 200 DEG C of insulation 2h, 210 DEG C of insulation 1h, obtain epoxy resin and consolidate
Compound；Or blend composition is placed in ceramic crucible, solidify 7 days at room temperature, obtain epoxy resin cured product.
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| CN201510426681.2A CN104945600B (en) | 2015-07-17 | 2015-07-17 | A kind of epoxy curing agent of the benzoxazine of list containing aliphatic cyclic amine type and preparation method thereof |
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| CN105622898B (en) * | 2015-12-28 | 2018-06-22 | 史铁钧 | Epoxy resin lalent solidifying agent, preparation method and its application of a kind of ring structure containing oxazine |
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