CN106242981A - A kind of new compound four [(p-aminophenyl epoxide) methyl] methane and synthetic method thereof - Google Patents
A kind of new compound four [(p-aminophenyl epoxide) methyl] methane and synthetic method thereof Download PDFInfo
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- CN106242981A CN106242981A CN201610517963.8A CN201610517963A CN106242981A CN 106242981 A CN106242981 A CN 106242981A CN 201610517963 A CN201610517963 A CN 201610517963A CN 106242981 A CN106242981 A CN 106242981A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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Abstract
Disclosing a kind of compound four [(acetparaminosalol phenoxy group) methyl] methane in the present invention, its molecular structural formula is as follows:
Description
Technical field
The invention belongs to epoxide resin material technical field, particularly relate to a kind of compound four [(p-aminophenyl epoxide) first
Base] methane and synthetic method thereof.
Background technology
Firming agent is component indispensable in epoxy formulations system, and plays decisive to the final performance of epoxy resin
Effect.Owing to the toughness of epoxy resin own is not good enough, traditional aromatic amine curing agent makes system solidification crosslink density higher, epoxy
Toughness worse, system need introduce toughener to improve toughness.Although traditional rubber toughened means are improving epoxy resin
The aspect of toughness obtains good effect, but reduces the thermostability of system while improving toughness, the most more and more grinds
Study carefully personnel to start with from MOLECULE DESIGN, introduce specific functional groups and carry out the epoxy curing agent of synthesizing new, and give solidfied material more
Many excellent process based prediction model.
Summary of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art and provides compound four
[(p-aminophenyl epoxide) methyl] methane and synthetic method thereof, this compound contains four amidos and stable benzene ring structure, amine
Base and phenyl ring are joined directly together, and are applied in the solidification of epoxy-resin systems, can fast-curing epoxy resin, and make solidfied material have
Good thermostability and mechanical property.
The present invention solves that the technical scheme that problem set forth above is used is:
A kind of compound four [(acetparaminosalol phenoxy group) methyl] methane, its molecular formula is C29H32O4N4, molecular structure
Formula is as follows:
The synthetic method of above-claimed cpd four [(p-aminophenyl epoxide) methyl] methane, mainly includes two steps:
The first step, season penta tetrabromo and acetaminophen obtained by the inferior synthetic reaction of William (williamson reaction)
Four [(acetparaminosalol phenoxy group) methyl] methane；
Second step, four [(acetparaminosalol phenoxy group) methyl] methane obtains four [(p-aminophenyl oxygen by hydrolysis
Base) methyl] methane.
Further, the inferior synthetic reaction of described William is: under an inert atmosphere, with season penta tetrabromo and acetaminophen
For initial reactant, in a solvent, alkali, catalyst, phase transfer catalyst existence condition under, reaction obtains four [(to acetyl
Amino-benzene oxygen) methyl] methane.
Further, described hydrolysis is: four [(acetparaminosalol phenoxy group) methyl] methane water in acid condition
After solution and to regulate its pH be 7～8, gained solid product is four [(p-aminophenyl epoxide) methyl] methane.
By such scheme, in the inferior synthetic reaction of described William, tetrabromo is 1:(4 with the mol ratio of acetaminophen season penta
～5).
By such scheme, in the inferior synthetic reaction of described William, reaction temperature is at 90 DEG C～110 DEG C, the response time be 12～
16h。
By such scheme, in the inferior synthetic reaction of described William, catalyst is potassium iodide, and phase transfer catalyst is the tetrabutyl
Ammonium bromide；The addition of described catalyst be season penta tetrabromo quality 1～3wt%, the addition of described phase transfer catalyst is
Season penta tetrabromo quality 0.3～0.5wt%.
By such scheme, in the inferior synthetic reaction of described William, alkali is the one in potassium carbonate, sodium carbonate, cesium carbonate etc..
By such scheme, the addition of alkali and the mol ratio of raw material acetaminophen in the inferior synthetic reaction of described William
For 1:1～3.Preferably, when described alkali selects potassium carbonate, the mol ratio of usual acetaminophen and potassium carbonate be 1:1～
1.25
By such scheme, in the inferior synthetic reaction of described William, inert atmosphere is nitrogen, helium, argon etc.；Described solvent
For the one in N-N dimethylformamide (DMF), N-N dimethyl acetylamide (DMAC), acetonitrile etc.；The addition of described solvent
According to reactant cumulative volume 4～6 times.
By such scheme, in described hydrolysis, acid is the mixed solution of hydrochloric acid, glacial acetic acid, the concentration of described hydrochloric acid
It is 8～10mol/L；Hydrochloric acid is 1:2～2.5 with the volume ratio of glacial acetic acid.Preferably, the consumption of described acid is four [(to acetyl
Amino-benzene oxygen) methyl] 5～10 times of methane volumetric.
By such scheme, in described hydrolysis, neutralize alkaline solutions such as using sodium hydroxide solution.Preferably, described
The mass fraction of sodium hydroxide solution be 20～30%.
By such scheme, in described hydrolysis, reaction temperature is 80～100 DEG C, and the response time is 10～12h.
Main chemical reactions equation involved in the present invention is as follows:
The first step:
Methane can be as the solidification of epoxy-resin systems for compound four [(p-aminophenyl epoxide) methyl] of the present invention
Agent is applied.
The cardinal principle of the present invention: the present invention, with simple and easy to get season penta tetrabromo as raw material, synthesizes according to williamson
The composition principle of method, prepares a kind of new symmetrical compound four [(p-acetylamino phenoxy group) containing four acetylaminos
Methyl] methane；It is hydrolyzed in acid condition available four [(p-aminophenyl epoxide) methyl] methane again.This kind of compound four
[(p-aminophenyl epoxide) methyl] methane contains four amidos, is applied in the solidification of epoxy-resin systems, can fast setting ring
Epoxy resins, the existence of aromatic ring also ensures that system has preferable thermostability.
Compared with prior art, the invention has the beneficial effects as follows:
1, four [(p-aminophenyl epoxide) methyl] methane of present invention design is as the novel aromatic amine curing agent of a class,
This compound contains four amidos and stable benzene ring structure, amido and phenyl ring are joined directly together, and is applied to epoxy-resin systems
In solidification, can fast-curing epoxy resin, and make solidfied material have good thermostability and mechanical property.
2, the preparation of four [(p-aminophenyl epoxide) methyl] methane of present invention design uses cheap season penta tetrabromo and right
Acetyl aminophenol is raw material, and reaction condition gentleness safety, productivity is higher, can reach 65%.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of four [(acetparaminosalol phenoxy group) methyl] methane molecule.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of four [(acetparaminosalol phenoxy group) methyl] methane molecule.
Fig. 3 is the infrared spectrogram of four [(p-aminophenyl epoxide) methyl] methane molecule.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with example, but the present invention is not only
It is limited only to the following examples.
Embodiment 1
A kind of compound four [(acetparaminosalol phenoxy group) methyl] methane, its molecular structural formula is as follows:
A kind of compound four [(p-aminophenyl epoxide) methyl] methane, its molecular formula is C29H32O4N4, molecular structural formula is such as
Shown in lower:
Above-claimed cpd synthetic method, step is as follows:
1) 1:5:5 weighs appropriate season penta tetrabromo, acetaminophen, potassium carbonate in molar ratio, according to the addition of catalyst
Amount weighs potassium iodide for the 1wt% of season penta tetrabromo quality, is season penta tetrabromo quality according to the addition of phase transfer catalyst
0.5wt% weighs tetrabutyl ammonium bromide, according to addition is reactant volume 4～6 times of addition DMF of solvent；
2) under nitrogen protection, acetaminophen, potassium carbonate, DMF and potassium iodide, tetrabutyl ammonium bromide are joined
In there-necked flask with agitating device, dropping is dissolved in the Ji Wusi bromine solutions of DMF, and temperature is risen to 100 DEG C 100 by heating
Back flow reaction 12h at DEG C；Reaction is poured in deionized water after terminating, and stands sucking filtration and obtains white solid, be after stirring
Four [(acetparaminosalol phenoxy group) methyl] methane.
3) hydrochloric acid solution and glacial acetic acid solution that concentration is 10mol/L are mixed, wherein hydrochloric acid solution and glacial acetic acid solution
Volume ratio be 1:2, add four [(acetparaminosalol phenoxy group) methyl] methane so that the volume of the acid of addition is four [(to second
Acylamino-phenoxy group) methyl] 8 times of methane volumetric, gained mixture adds in there-necked flask and reacts 10h at 80 DEG C；Reaction knot
Shu Hou, with the sodium hydroxide solution regulation pH that mass fraction is 30% to there is precipitation, is collected by filtration precipitation, obtains Huang after drying
Brown solid, is four [(p-aminophenyl epoxide) methyl] methane.
Embodiment 2
Compound four [(p-aminophenyl epoxide) methyl] methane, its synthetic method is as follows:
1) 1:5:5 weighs appropriate season penta tetrabromo, acetaminophen, potassium carbonate in molar ratio, according to the addition of catalyst
Amount weighs potassium iodide for the 3wt% of season penta tetrabromo quality, is season penta tetrabromo quality according to the addition of phase transfer catalyst
0.3wt% weighs tetrabutyl ammonium bromide, according to addition is reactant volume 4～6 times of addition DMF of solvent；
2) under nitrogen protection, acetaminophen, potassium carbonate, DMF and potassium iodide, tetrabutyl ammonium bromide are joined
In there-necked flask with agitating device, dropping is dissolved in the Ji Wusi bromine solutions of DMF, and temperature is risen to 110 DEG C 110 by heating
Back flow reaction 12h at DEG C, goes out white solid by deionized water extract and separate, is four [(acetparaminosalol phenoxy group) methyl] first
Alkane.
3) hydrochloric acid solution and glacial acetic acid solution that concentration is 10mol/L are mixed, wherein hydrochloric acid solution and glacial acetic acid solution
Volume ratio be 1:2.5, add four [(acetparaminosalol phenoxy group) methyl] methane so that the volume of the acid of addition is four [(right
Acetylamino phenoxy group) methyl] 9 times of methane volumetric, gained mixture adds in there-necked flask and reacts 11h at 90 DEG C；Reaction
After end, with sodium hydroxide solution that mass fraction is 25% regulation pH to precipitation occurs, precipitation is collected by filtration, after drying and get final product
To brown solid four [(p-aminophenyl epoxide) methyl] methane.
Embodiment 3
Compound four [(p-aminophenyl epoxide) methyl] methane, its synthetic method is as follows:
1) 1:5:5.25 weighs appropriate season penta tetrabromo, acetaminophen, potassium carbonate, adding according to catalyst in molar ratio
Entering amount is season penta 2wt% of tetrabromo quality to weigh potassium iodide, is season penta tetrabromo quality according to the addition of phase transfer catalyst
0.4wt% weighs tetrabutyl ammonium bromide, according to addition is reactant volume 4～6 times of addition DMF of solvent；
2) under nitrogen protection, acetaminophen, potassium carbonate, DMF and potassium iodide, tetrabutyl ammonium bromide are joined
In there-necked flask with agitating device, dropping is dissolved in the Ji Wusi bromine solutions of DMF, and temperature is risen to 90 DEG C at 90 DEG C by heating
Lower back flow reaction 12h, obtains white solid, is four [(acetparaminosalol phenoxy group) methyl] methane.
3) by hydrochloric acid solution that concentration is 9mol/L and glacial acetic acid solution mixing, wherein hydrochloric acid solution and glacial acetic acid solution
Volume ratio is 1:2.2, adds four [(acetparaminosalol phenoxy group) methyl] methane so that the volume of the acid of addition is four [(to second
Acylamino-phenoxy group) methyl] 10 times of methane volumetric, gained mixture adds in there-necked flask and reacts 12h at 100 DEG C；Reaction
After end, with sodium hydroxide solution that mass fraction is 30% regulation pH to precipitation occurs, precipitation is collected by filtration, after drying and get final product
To brown solid four [(p-aminophenyl epoxide) methyl] methane.
Fig. 1 is the infrared spectrogram of four [(acetparaminosalol phenoxy group) methyl] methane molecule, analyzes such as table 1, it was demonstrated that press
The product obtained according to the method for the invention is four [(acetparaminosalol phenoxy group) methyl] methane.
Table 1
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of four [(acetparaminosalol phenoxy group) methyl] methane molecule, and solvent uses deuterated diformazan
Base sulfoxide (DMSO) is analyzed as shown in table 2, the integral area ratio of absworption peak 1 to 5 and four [(acetparaminosalol phenoxy group) first
Base] on relevant position, the number of H coincide in methane molecule structure, it was demonstrated that and gained material is four [(acetparaminosalol phenoxy group) first
Base] methane.
Table 2
Fig. 3 is the infrared spectrogram of four [(p-aminophenyl epoxide) methyl] methane molecule, analyzes such as table 3, it is therefore evident that press
The product obtained according to the method for the invention is four [(p-aminophenyl epoxide) methyl] methane.
Table 3
Application examples:
Four [(p-aminophenyl epoxide) methyl] methane that the present invention the prepares following institute of curing mechanism to epoxy resin
Show.Under conditions of without accelerator, primary amine groups and epoxy reaction on four [(p-aminophenyl epoxide) methyl] methane generate secondary
Amine, the secondary amine of generation and epoxy reaction generate tertiary amine, and the hydroxyl generated also can and epoxy reaction, there is acceleration reaction
The tendency carried out.
Compound four [(p-aminophenyl epoxide) methyl] methane is at the application process of epoxy-resin systems, and its step is as follows:
(1) according to the mass fraction, E51 epoxy resin 100 parts is weighed, four [(p-aminophenyl epoxide) methyl] 35 parts of methane,
Stir evenly, use glass fiber dipped compression molding, gained epoxy resin composition is heated to 120 DEG C of solidification 4h, 150 DEG C of solidifications
4h；(2) solidification afterwards: step (1) products therefrom is solidified 2h in 180 DEG C, this firming agent can fast-curing epoxy resin, and make solid
Compound has good thermostability and mechanical property.
The above is only the preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
Saying, without departing from the concept of the premise of the invention, it is also possible to make some modifications and variations, these broadly fall into the present invention's
Protection domain.
Claims (10)
1. compound four [(acetparaminosalol phenoxy group) methyl] methane, its molecular formula is C29H32O4N4, molecular structural formula
As follows:
2. the synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane, it is characterised in that mainly include two steps:
The first step, season penta tetrabromo and acetaminophen obtain four [(acetylaminobenzene oxygen by the inferior synthetic reaction of William
Base) methyl] methane；
Second step, four [(acetparaminosalol phenoxy group) methyl] methane obtains four [(p-aminophenyl epoxide) first by hydrolysis
Base] methane.
The synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane the most according to claim 2, its feature exists
In the inferior synthetic reaction of described William it is: under an inert atmosphere, with season penta tetrabromo and acetaminophen as initial reactant,
In solvent, alkali, catalyst, phase transfer catalyst existence condition under, reaction obtain four [(acetparaminosalol phenoxy group) first
Base] methane.
The synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane the most according to claim 3, its feature exists
In the inferior synthetic reaction of described William, tetrabromo is 1:(4～5 with the mol ratio of acetaminophen season penta).
The synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane the most according to claim 3, its feature exists
In the inferior synthetic reaction of described William, reaction temperature is at 90 DEG C～110 DEG C, and the response time is 12～16h.
The synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane the most according to claim 3, its feature exists
In the inferior synthetic reaction of described William, catalyst is potassium iodide, and phase transfer catalyst is tetrabutyl ammonium bromide；Described catalyst
Addition be season penta tetrabromo quality 1～3wt%, the addition of described phase transfer catalyst be season penta tetrabromo quality 0.3
～0.5wt%.
The synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane the most according to claim 3, its feature exists
In the inferior synthetic reaction of described William, the addition of alkali and the mol ratio of raw material acetaminophen are 1:1～3.
The synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane the most according to claim 2, its feature exists
In described hydrolysis it is: after four [(acetparaminosalol phenoxy group) methyl] methane hydrolyzes in acid condition and regulate its pH and be
7～8, gained solid product is four [(p-aminophenyl epoxide) methyl] methane.
The synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane the most according to claim 8, its feature exists
In described hydrolysis, acid is the mixed solution of hydrochloric acid, glacial acetic acid, and hydrochloric acid is 1:2～2.5 with the volume ratio of glacial acetic acid；Institute
The concentration of the hydrochloric acid stated is 8～10mol/L.
The synthetic method of compound four [(p-aminophenyl epoxide) methyl] methane the most according to claim 8, its feature exists
In described hydrolysis, reaction temperature is 80～100 DEG C, and the response time is 10～12h.
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| CN102933565A (en) * | 2010-06-10 | 2013-02-13 | 帝人株式会社 | Cyclic carbodiimide compound |
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2016
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|---|---|---|---|---|
| US4870206A (en) * | 1987-07-08 | 1989-09-26 | Bayer Aktiengesellschaft | Aromatic polyisocyanates, their preparation and use as components for adhesives |
| US20040075723A1 (en) * | 2002-09-04 | 2004-04-22 | Xerox Corporation | Alkylated urea and triaminotriazine compounds and phase change inks containing same |
| CN1918117A (en) * | 2004-03-29 | 2007-02-21 | 富士胶片株式会社 | Dendron and dendrimer, method of producing the same, and method of producing a thioacetal compound |
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Application publication date: 20161221 |