CN109485916A - A kind of synthesis and application of Aminopyrazine based flame retardant - Google Patents
A kind of synthesis and application of Aminopyrazine based flame retardant Download PDFInfo
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- CN109485916A CN109485916A CN201811382969.4A CN201811382969A CN109485916A CN 109485916 A CN109485916 A CN 109485916A CN 201811382969 A CN201811382969 A CN 201811382969A CN 109485916 A CN109485916 A CN 109485916A
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- Prior art keywords
- aminopyrazine
- flame retardant
- based flame
- synthetic method
- epoxy resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The synthesis and application of a kind of Aminopyrazine based flame retardant disclosed by the invention, including a kind of compound A, chemical structural formula are as follows:, apply to compound A as fire retardant in the fire-retardant attribute for increasing epoxy resin, good flame retardation effect, synthesis process side reaction is few, and yield is high.
Description
Technical field
The present invention relates to epoxide resin material fields, and in particular to a kind of synthesis and application of Aminopyrazine based flame retardant.
Background technique
Epoxy resin (EP) is used as a kind of the most widely used thermoset copolymer material, has excellent electrical isolation
Property, dimensional stability, high thermal stability, low-shrinkage, strong bonding and mechanical endurance etc. are widely used in electronics electricity
Device, automobile, packaging, printed circuit board, the fields such as adhesive and surface covering, but since its inflammability limits it in many
Application in field.Therefore, it is vital for assigning the good anti-flammability of EP.
In order to improve the flame retardant property of epoxy resin, common method is addition fire retardant.Since traditional halogen system is fire-retardant
There are secondary injuries such as thickness, toxic gas discharges when agent is burnt, constitute a serious threat to personal safety, therefore design novel nothing
Halogen fire retardant is particularly important, and halogen-free flame retardants in the prior art includes no phosphorus flame retardant, nitrogenated flame retardant and expansion
Type fire retardant etc., synthesis step is complicated, and side reaction is more, and flame retarding efficiency is poor compared with halogen containing flame-retardant effect.
Therefore, it is badly in need of synthesizing one kind, the halogen-free flame retardants that flame retarding efficiency is high, side reaction is few.
Summary of the invention
To solve the above problems, the present invention provides the synthesis and application of a kind of Aminopyrazine based flame retardant, fire retardant resistance
Fuel efficiency fruit is good, and synthesis process side reaction is few, and yield is high.
The technical solution that the present invention solves is to provide a kind of Aminopyrazine based flame retardant, which is characterized in that the amino pyrrole
Piperazine based flame retardant includes compound A, and the molecular structural formula of the compound A is as follows:
,
A kind of synthetic method of Aminopyrazine based flame retardant is also provided, which comprises the following steps:
(1) using alcohol as solvent, the condensation reaction of Aminopyrazine and salicylide generation amino, aldehyde radical synthesizes intermediate product；
(2) using alcohol as solvent, the intermediate product and DOPO carry out addition reaction, obtain compound A.
Preferably, the reactant Aminopyrazine, salicylide, DOPO molar ratio be 1:1:1 ~ 2.
Preferably, the step (1), step (2) reaction temperature be 50-65 DEG C.
Preferably, the reaction time of the step (1) is 3-5h.
Preferably, the reaction time of the step (2) is 2-4h.
Preferably, the alcoholic solvent of the step (1) is ethyl alcohol.
It preferably, include epoxy resin, Aminopyrazine based flame retardant, curing agent.
It is worth noting that, the specific synthesis step of Aminopyrazine based flame retardant of the present invention is as follows: in the guarantor of nitrogen
Under shield, by Aminopyrazine and salicylide in 50 ~ 65 DEG C of magnetic agitation 3-5h, and to condense than being dissolved in ethyl alcohol for the ratio of 1:1
Reflux；It by obtained solution cooling and filters, products therefrom ethanol washing will be filtered, it is dry to be placed in vacuum oven
Dry 10-12h obtains yellow solid, as intermediate product；Intermediate product is dissolved in ethyl alcohol, is slowly added dropwise and Aminopyrazine
Molar ratio is the DOPO of 1:1, magnetic agitation 2-4h at 50-65 DEG C, gained precipitating is filtered, and use ethanol aqueous wash
It washs, is placed in the dry 10-12h of vacuum oven, obtains white solid, i.e., the described compound A, below with DHABP flame retardant instead.
Although Aminopyrazine is inflammable compound, the synergistic effect of N-P, possible cause can be generated after combining with DOPO
It is nucleophilic attack formation phosphorous-nitrogen compounds phosphamide of the nitrogen-atoms in nitrogen compound to the phosphorus atoms in phosphorus compound, phosphinylidyne
Amine can play the role of lewis acid and crosslinking agent.To make the carbon coke of epoxy resin thermal cracking have higher crosslinking close
Degree, plays heat-insulated effect.Some nitrogenous non-combustible gas, which are discharged, when the pyridine ring in product is burnt simultaneously dilutes combustible gas
Body plays the role of retarded combustion.
Compared with prior art, the Aminopyrazine based flame retardant prepared by the present invention, can be used as additive and is added to epoxy
In resin, its anti-flammability is improved, and flame retarding efficiency is high, synthesis process side reaction is few, and yield is high.
Detailed description of the invention
Fig. 1 is the reaction equation of Aminopyrazine based flame retardant of the present invention；
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of 1 Aminopyrazine based flame retardant of embodiment；
Fig. 3 is that the nuclear-magnetism phosphorus of 1 Aminopyrazine based flame retardant of embodiment composes spectrogram.
Specific embodiment
Following is a specific embodiment of the present invention in conjunction with the accompanying drawings, technical scheme of the present invention will be further described,
However, the present invention is not limited to these examples.
Embodiment 1
The preparation method of Aminopyrazine based flame retardant:
1) 2.50 g(26.5 mmol are accurately weighed) Aminopyrazine, 30 ml ethyl alcohol are in 100 ml three neck round bottom flask, with perseverance
3.2 g (26.5 mmol) salicylide (20 ml ethyl alcohol) solution, the magnetic force at 65 DEG C is slowly added dropwise in pressure loophole thereto
It is stirred to react 4 h；After reaction, by obtained solution cooling filter, will filter gained intermediate product ethyl alcohol into
Row washing, puts and dries 12h in a vacuum drying oven, obtain 14.84 g of yellow solid, as intermediate product.
2) intermediate product is dissolved in 30.0 ml ethyl alcohol, adds DOPO(26.5 mmol, 5.728 g), stirs molten
3 h of liquid, reaction temperature are 60 DEG C, and upper step is reacted gained precipitating and is filtered, is washed with the mixture of second alcohol and water,
12 h are dried in vacuo at 80 DEG C, obtaining white solid 28.7g(yield is 98.7%) as final product.
As shown in Figure 2, chemical shift can belong to the hydrogen atom on aromatic ring at the peak of 6.4-8.2ppm.The peak of 6.2ppm is returned
Belong to the hydrogen atom on methylene.2.5ppm and 3.2ppm is the chemical shift of solvent DMSO and water respectively.In addition, its peak
Area and corresponding numbers of hydrogen atoms are essentially identical, illustrate to synthesize successfully.
From the figure 3, it may be seen that only occurring two chemical shifts in phosphorus spectrogram is separated by closer two peaks, this can belong to one kind
Phosphorus atoms, this phenomenon are generated due to chiral carbon, this also has report in fire proofing of the others containing DOPO
Road illustrates to synthesize successfully.
Embodiment 2
The measure of merit of Aminopyrazine based flame retardant:
100.00 g epoxy resin, 6.60 g DHABP fire retardants and 26.00 g curing agent are sequentially added in flask, 90
At DEG C after mixing evenly, it pours into mold, is cooled to room temperature, it is solid to get epoxy resin to solidify 2 h at 100 and 150 DEG C respectively
Compound, fire retardant additive amount 5%, phosphorus content 0.3%, oxygen index (OI) test result are 33.4%, and vertical combustion grade is UL-94 V-
1 grade.
It is worth noting that the limit oxygen index in embodiment is using HC-2C type oxygen index measurer according to GB/T
2406-1993 is tested, and vertical combustion is tested using CZF-2 type Vertical combustion instrument according to GB/T2408-1996.
Embodiment 3
The measure of merit of Aminopyrazine based flame retardant:
100.00 g epoxy resin, 11.00 g DHABP fire retardants and 26.00 g curing agent are sequentially added in flask,
At 90 DEG C after mixing evenly, it pours into mold, is cooled to room temperature, solidify 2 h at 100 and 150 DEG C respectively to get epoxy resin
Solidfied material, fire retardant additive amount 8%, phosphorus content 0.6%, oxygen index (OI) test result are 34.0%, and vertical combustion grade is UL-94
V-0 grades.
It is worth noting that the limit oxygen index in embodiment is using HC-2C type oxygen index measurer according to GB/T
2406-1993 is tested, and vertical combustion is tested using CZF-2 type Vertical combustion instrument according to GB/T2408-1996.
Embodiment 4
100.00 g epoxy resin, 14.00 g DHABP fire retardants and 26.00 g curing agent are sequentially added in flask,
At 90 DEG C after mixing evenly, it pours into mold, is cooled to room temperature, solidify 2 h at 100 and 150 DEG C respectively to get epoxy resin
Solidfied material, fire retardant additive amount 10%, phosphorus content 0.77%, oxygen index (OI) test result are 34.3%, and vertical combustion grade is UL-
94 V-0 grades.
It is worth noting that the limit oxygen index in embodiment is using HC-2C type oxygen index measurer according to GB/T
2406-1993 is tested, and vertical combustion is tested using CZF-2 type Vertical combustion instrument according to GB/T2408-1996.
Embodiment 5
100.00 g epoxy resin, 26.00 g curing agent are sequentially added in flask, at 90 DEG C after mixing evenly, pour into mould
It in tool, is cooled to room temperature, solidifies 2 h at 100 and 150 DEG C respectively to get epoxy resin cured product, oxygen index (OI) test result is
25.8%, vertical combustion grade is NR.
It is not directed to place above, is suitable for the prior art.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (8)
1. a kind of Aminopyrazine based flame retardant, which is characterized in that the Aminopyrazine based flame retardant includes compound A, describedization
The molecular structural formula for closing object A is as follows:
。
2. a kind of synthetic method of Aminopyrazine based flame retardant, which comprises the following steps:
Using alcohol as solvent, the condensation reaction of Aminopyrazine and salicylide generation amino, aldehyde radical synthesizes intermediate product:
；
Using alcohol as solvent, the intermediate product and DOPO carry out addition reaction, obtain compound A:
。
3. a kind of synthetic method of Aminopyrazine based flame retardant according to claim 2, which is characterized in that the reactant
Aminopyrazine, salicylide, DOPO molar ratio be 1:1:1 ~ 2.
4. a kind of synthetic method of Aminopyrazine based flame retardant according to claim 2, which is characterized in that the step
(1), the reaction temperature of step (2) is 50-65 DEG C.
5. a kind of synthetic method of Aminopyrazine based flame retardant according to claim 2, which is characterized in that the step
(1) reaction time is 3-5h.
6. a kind of synthetic method of Aminopyrazine based flame retardant according to claim 2, which is characterized in that the step
(2) reaction time is 2-4h.
7. a kind of synthetic method of Aminopyrazine based flame retardant according to claim 2, which is characterized in that the step
(1) alcoholic solvent is ethyl alcohol.
8. a kind of epoxy resin cured product, which is characterized in that include epoxy resin, the Aminopyrazine based flame retardant, curing agent.
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| CN201811382969.4A CN109485916A (en) | 2018-11-20 | 2018-11-20 | A kind of synthesis and application of Aminopyrazine based flame retardant |
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| CN201811382969.4A CN109485916A (en) | 2018-11-20 | 2018-11-20 | A kind of synthesis and application of Aminopyrazine based flame retardant |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041370A (en) * | 2019-05-17 | 2019-07-23 | 武汉工程大学 | A kind of preparation method and applications of the efficient flame-retarding agent containing DOPO and Aminopyrazine structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0096125A1 (en) * | 1982-06-09 | 1983-12-21 | Merck & Co. Inc. | Amino and amido derivatives of chloro nitro amino and alkylamino pyrazines useful as adjuncts to radiation therapy |
| CN103012484A (en) * | 2012-12-24 | 2013-04-03 | 清华大学深圳研究生院 | Phosphorous benzoxazine resin, preparation method and application |
| CN104693421A (en) * | 2015-03-27 | 2015-06-10 | 厦门大学 | Self-inflaming-retarding epoxy resin curing agent containing phosphorus-nitrogen and preparation method thereof |
| CN106749413A (en) * | 2016-11-24 | 2017-05-31 | 福建师范大学 | Using the preparation method of the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy |
-
2018
- 2018-11-20 CN CN201811382969.4A patent/CN109485916A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0096125A1 (en) * | 1982-06-09 | 1983-12-21 | Merck & Co. Inc. | Amino and amido derivatives of chloro nitro amino and alkylamino pyrazines useful as adjuncts to radiation therapy |
| CN103012484A (en) * | 2012-12-24 | 2013-04-03 | 清华大学深圳研究生院 | Phosphorous benzoxazine resin, preparation method and application |
| CN104693421A (en) * | 2015-03-27 | 2015-06-10 | 厦门大学 | Self-inflaming-retarding epoxy resin curing agent containing phosphorus-nitrogen and preparation method thereof |
| CN106749413A (en) * | 2016-11-24 | 2017-05-31 | 福建师范大学 | Using the preparation method of the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy |
Non-Patent Citations (3)
| Title |
|---|
| ABDULLAH M.ASIRI: "Synthesis of Some New Anils: Part 1. Reaction of 2-Hydroxy-benzaldehyde and 2-Hydroxynaphthaldehyde with 2-Aminopyridene and 2-Aminopyrazine", 《MOLECULES》 * |
| PAN WANG: "Flame-retarding epoxy resin with an efficient P/N/S-containing flame retardant: Preparation, thermal stability, and flame retardance", 《POLYMER DEGRADATION AND STABILITY》 * |
| RONGKUN JIAN: "Effect of a novel P/N/S-containing reactive flame retardant on curing behavior, thermal and flame-retardant properties of epoxy resin", 《JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041370A (en) * | 2019-05-17 | 2019-07-23 | 武汉工程大学 | A kind of preparation method and applications of the efficient flame-retarding agent containing DOPO and Aminopyrazine structure |
| CN110041370B (en) * | 2019-05-17 | 2021-08-06 | 武汉工程大学 | Preparation method and application of efficient flame retardant containing DOPO and aminopyrazine structures |
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