CN104927060B - A kind of expansion type flame retardant and preparation method thereof - Google Patents
A kind of expansion type flame retardant and preparation method thereof Download PDFInfo
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- CN104927060B CN104927060B CN201510066669.5A CN201510066669A CN104927060B CN 104927060 B CN104927060 B CN 104927060B CN 201510066669 A CN201510066669 A CN 201510066669A CN 104927060 B CN104927060 B CN 104927060B
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- 0 **(C*1[N+]c2nc(N)nc(N)n2)P1(C[N+](*)*N(*)C(*)(*)*)=O Chemical compound **(C*1[N+]c2nc(N)nc(N)n2)P1(C[N+](*)*N(*)C(*)(*)*)=O 0.000 description 1
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Abstract
The present invention provides a kind of expansion type flame retardant and preparation method thereof, and this method includes：1) ortho phosphorous acid sodium dihydrogen, organic amine A are dissolved in concentrated hydrochloric acid respectively, inert gas is imported with magnetic agitation, and paraformaldehyde solution is slowly dropped in above-mentioned solution, after completion of dropping, after the reaction of certain temperature and time, reaction product B is obtained；(2) concentrated hydrochloric acid solution of dissolving organic amine C and paraformaldehyde, is instilled into reaction system, reaction product B is blocked, after completion of dropping, continue to react 2-12 hours, reaction product D after being blocked, cooling, organic solvent extraction, filtering, washing, drying obtain white powder shaped polymer；(3) the white powder shaped polymer obtained in (2) is dissolved in the aqueous solution containing melamine and neutralized, after neutralizing temperature reaction 2-5 hours, suction filtration is washed, and drying obtains expansion type flame retardant.Present invention process is simple, yield is higher.
Description
Technical field
The present invention relates to technical field of flame retardant, more particularly to a kind of expansion type flame retardant and preparation method thereof.
Background technology
As the booming life given people of high polymer material brings many facilities, people are enjoying high score scarabaeidae
While the facility that skill is brought, the great disaster brought by the inflammability of high polymer material is also subjected to, therefore improve high
The flame-retarded technology level of molecular material, is one of focus of current scientific and technological circle's research.Fire retardant, energy are introduced in high polymer material
Enough reduce the fire risk of material.Traditional small molecule fire retardant, is used widely due to easy to process, but small point
It is low to there is flame retarding efficiency in sub- fire retardant, and addition is big, poor with material compatibility, the shortcoming of the performance such as machinery, electricity of influence material,
It is restricted its application.The macromolecular fire retardant of recent domestic research synthesis is right because its compatibility with material is better
The physical property influence of material is smaller, and receives much concern.
The content of the invention
It is an object of the invention to provide a kind of macromolecular expansion type flame retardant and preparation method thereof, by improving fire retardant
The fire-retardant of polymer is improved with the compatibility of high polymer material and using the synergistic fire retardation between a variety of ignition-proof elements
Performance, solve this kind of compound is used in multiple polymers as flame-retardant additive.
A kind of expansion type flame retardant, shown in following 1 formula of its structural formula or 2 formulas or 3 formulas：
Wherein R1For aliphatic chain or fragrant chain；
Wherein R1, R2, R3For aliphatic chain or fragrant chain；
Wherein R1, R2For aliphatic chain or fragrant chain.
A kind of preparation method of expansion type flame retardant, comprises the following steps：
(1) ortho phosphorous acid sodium dihydrogen, organic amine A are dissolved in concentrated hydrochloric acid respectively, imported and magnetic agitation in inert gas
Under, the hydrochloric acid solution for being dissolved with paraformaldehyde is slowly dropped in above-mentioned solution, after completion of dropping, in certain temperature and time
Reaction after, obtain reaction product B；
(2) concentrated hydrochloric acid solution of dissolving organic amine C and paraformaldehyde, is instilled into reaction system, reaction product B is carried out
After end-blocking, completion of dropping, continue to react certain hour, reaction product D after being blocked, the solvent in cooling, evaporation reaction bulb,
Washed after cooling through ethanol, dry, obtain white powder shaped polymer；
(3) the white powder shaped polymer obtained in (2) is dissolved in being carried out in the aqueous solution containing melamine
With neutralize after temperature reaction 2-5 hour, suction filtration, washing is dried, obtains expansion type flame retardant.
Further, in the preparation method of expansion type flame retardant as described above, step 1, the ortho phosphorous acid sodium dihydrogen,
Organic amine A, the mol ratio of paraformaldehyde are 1：1：(2—4).
Further, in the preparation method of expansion type flame retardant as described above, step 2, the organic amine C and poly first
The mol ratio of aldehyde is 1：2.
Further, the preparation method of expansion type flame retardant as described above, prepares intermediate reaction product B and reaction is produced
Thing D reaction temperature is 70-150 DEG C, and the reaction time is 2-12 hours.
Further, the preparation method of expansion type flame retardant as described above, the reaction temperature of neutralization reaction is 20-100
DEG C, the reaction time of neutralization reaction is 2-5 hours.
Further, the preparation method of expansion type flame retardant as described above, the solution pH value of neutralization reaction is controlled in 4-
6。
Further, the preparation method of expansion type flame retardant as described above, the organic amine A be a kind of unary primary amine or
Binary secondary amine.
Further, the preparation method of expansion type flame retardant as described above, the organic amine C is unitary secondary amine.
The expansion type flame retardant that the present invention is provided can be used in multiple polymers, to improve the fire resistance of polymer.This
Invented technology working condition is simple, yield is higher, last handling process is easy.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below technical scheme in the present invention carry out it is clear
Chu, it is fully described by, it is clear that described embodiment is a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
The expansion type flame retardant preparation method that the present invention is provided is：First by organic amine A, ortho phosphorous acid sodium dihydrogen and poly
Formaldehyde reacts in concentrated hydrochloric acid synthesizes linear macromolecule B, wherein, organic amine A, ortho phosphorous acid sodium dihydrogen and paraformaldehyde rub
You are than being 1：1：(2-4), under this proportioning, side reaction is few, and product purity is high, and too high or too low proportioning will all make
Product purity is obtained to decline.Then end-blocking is carried out to B with organic amine C and paraformaldehyde and synthesizes D；Finally use in melamine and D
Obtain a kind of macromolecular expansion type flame retardant.Raw material organic amine A for common a kind of unary primary amine or binary secondary amine or it is a kind of with
On unary primary amine or binary secondary amine arbitrary proportion mixture, and organic amine C be a kind of unitary secondary amine.Synthesized in preparation process
Macromolecule B and D reaction temperature are preferably 70-150 DEG C, and the reaction time is preferably 2-12 hours.The reaction temperature of neutralization reaction
Preferably 20-100 DEG C of degree, the reaction time is preferably 2-5 hours, and the solution pH value of neutralization reaction is preferably 4-6, and pH value is too high
Either too low all side reaction to be increased, product purity declines, therefore, and the present invention is by pH value control in 4-6.
A kind of preparation method of described macromolecular expansion type flame retardant, the consumption of its solvent concentrated hydrochloric acid is time phosphorous
10-100 times of acid dihydride sodium consumption.
Embodiment 1：
To equipped with thermometer, nitrogen importing, 100ml constant pressure funnels, magneton and reflux condensing tube and tail gas absorption dress
In the 500ml four-hole boiling flasks put add piperazine (8.614g, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) and
200ml concentrated hydrochloric acids, under nitrogen protection and magnetic agitation, will be dissolved with the dense salt of 50ml of paraformaldehyde (9.009g, 0.3mol)
Acid, is added in constant pressure funnel, is slowly dropped in four-hole boiling flask, after completion of dropping, is warming up to 70 DEG C and continues to react 12 small
When；
After reaction terminates, dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is taken to be dissolved in
In 50ml concentrated hydrochloric acids, it is added in constant pressure funnel.Under nitrogen protection and magnetic agitation, it is slowly dropped in four-hole boiling flask,
Continue to react 5 hours at 100 DEG C, continue logical N2Room temperature is down to, the solvent in reaction bulb is then evaporated, 100ml is used after cooling
Ethanol washs to obtain white solid, and 6 hours are dried in vacuo at 60 DEG C, 19.63g products, yield 89% is obtained；
Then 8 grams of products are taken, are dissolved in 20 milliliters of distilled water containing melamine, it is 4 to control solution pH value, is risen
Temperature is reacted after 5 hours to 80 DEG C, suction filtration, is washed, and drying obtains white solid powder shape macromolecular expansion type flame retardant.
Embodiment 2：
To equipped with thermometer, nitrogen importing, 100ml constant pressure funnels, magneton and reflux condensing tube and tail gas absorption dress
In the 500ml four-hole boiling flasks put add homopiperazine (10.218g, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) and
200ml concentrated hydrochloric acids, under nitrogen protection and magnetic agitation, will be dissolved with the dense salt of 50ml of paraformaldehyde (6.006g, 0.2mol)
Acid, is added in constant pressure funnel, is slowly dropped in four-hole boiling flask, after completion of dropping, is warming up to 150 DEG C and continues to react 2 small
When；
After reaction terminates, dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is taken to be dissolved in
In 50ml concentrated hydrochloric acids, it is added in constant pressure funnel, under nitrogen protection and magnetic agitation, is slowly dropped in four-hole boiling flask,
Continue to react 5 hours at 150 DEG C, continue logical N2Room temperature is down to, the solvent in reaction bulb is then evaporated, 100ml is used after cooling
Ethanol washs to obtain white solid, and 6 hours are dried in vacuo at 60 DEG C, 22.03g products, yield 92% is obtained；
Then 8 grams of products are taken, are dissolved in 20 milliliters of distilled water, melamine is added, it is 6 to control solution pH value,
It is warming up to after 100 DEG C of 5 hours of reaction, suction filtration is washed, drying obtains white solid powder shape macromolecular expansion type flame retardant.
Embodiment 3：
To equipped with thermometer, nitrogen importing, 100ml constant pressure funnels, magneton and reflux condensing tube and tail gas absorption dress
In the 500ml four-hole boiling flasks put add methylamine (3.106g, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) and
200ml concentrated hydrochloric acids, under nitrogen protection and magnetic agitation, will be dissolved with the dense salt of 50ml of paraformaldehyde (12.012g, 0.4mol)
Acid, is added in constant pressure funnel, is slowly dropped in four-hole boiling flask, after completion of dropping, is warming up to 100 DEG C and continues to react 12 small
When；
After reaction terminates, dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is taken to be dissolved in
In 50ml concentrated hydrochloric acids, it is added in constant pressure funnel.Under nitrogen protection and magnetic agitation, it is slowly dropped in four-hole boiling flask,
Continue to react 10 hours at 100 DEG C, continue logical N2Room temperature is down to, the solvent in reaction bulb is then evaporated, 100ml is used after cooling
Ethanol washs to obtain white solid, and 6 hours are dried in vacuo at 60 DEG C, 15.23g products, yield 92.3% is obtained；
Then 8 grams of products are taken, are dissolved in 20 milliliters of distilled water, melamine is added, it is 5 to control solution pH value,
It is warming up to after 80 DEG C of 5 hours of reaction, suction filtration is washed, drying obtains white solid powder shape macromolecular expansion type flame retardant.
Embodiment 4：
To equipped with thermometer, nitrogen importing, 100ml constant pressure funnels, magneton and reflux condensing tube and tail gas absorption dress
Addition cyclohexylmethylamine (11.320g, 0.1mol) in the 500ml four-hole boiling flasks put, ortho phosphorous acid sodium dihydrogen (8.798g,
0.1mol) with 200ml concentrated hydrochloric acids, under nitrogen protection and magnetic agitation, paraformaldehyde (9.009g, 0.3mol) will be dissolved with
50ml concentrated hydrochloric acids, are added in constant pressure funnel, are slowly dropped in four-hole boiling flask, after completion of dropping, are warming up to 100 DEG C and continue anti-
Answer 10 hours；
After reaction terminates, dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is taken to be dissolved in
In 50ml concentrated hydrochloric acids, it is added in constant pressure funnel, under nitrogen protection and magnetic agitation, is slowly dropped in four-hole boiling flask,
Continue to react 10 hours at 100 DEG C, continue logical N2Room temperature is down to, the solvent in reaction bulb is then evaporated, 100ml is used after cooling
Ethanol washs to obtain white solid, and 6 hours are dried in vacuo at 60 DEG C, 21.28g products, yield 84.32% is obtained；
Then 8 grams of products are taken, are dissolved in 20 milliliters of distilled water, melamine is added, it is 6 to control solution pH value,
It is warming up to after 80 DEG C of 5 hours of reaction, suction filtration is washed, drying obtains white solid powder shape macromolecular expansion type flame retardant.
Embodiment 5：
To equipped with thermometer, nitrogen importing, 100ml constant pressure funnels, magneton and reflux condensing tube and tail gas absorption dress
In the 500ml four-hole boiling flasks put add benzene methanamine (10.816g, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) and
200ml concentrated hydrochloric acids, under nitrogen protection and magnetic agitation, will be dissolved with the dense salt of 50ml of paraformaldehyde (9.009g, 0.3mol)
Acid, is added in constant pressure funnel, is slowly dropped in four-hole boiling flask, after completion of dropping, is warming up to 100 DEG C and continues to react 10 small
When；
After reaction terminates, dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is taken to be dissolved in
In 50ml concentrated hydrochloric acids, it is added in constant pressure funnel.Under nitrogen protection and magnetic agitation, it is slowly dropped in four-hole boiling flask,
Continue to react 10 hours at 100 DEG C, continue logical N2Room temperature is down to, the solvent in reaction bulb is then evaporated, 100ml is used after cooling
Ethanol washs to obtain white solid, and 6 hours are dried in vacuo at 60 DEG C, 20.05g products, yield 82.85% is obtained；
Then 8 grams of products are taken, are dissolved in 20 milliliters of distilled water, melamine is added, it is 6 to control solution pH value,
It is warming up to after 80 DEG C of 5 hours of reaction, suction filtration is washed, drying obtains white solid powder shape macromolecular expansion type flame retardant.
Embodiment 6：
To equipped with thermometer, nitrogen importing, 100ml constant pressure funnels, magneton and reflux condensing tube and tail gas absorption dress
Addition diethyl ethylenediamine (11.620g, 0.1mol) in the 500ml four-hole boiling flasks put, ortho phosphorous acid sodium dihydrogen (8.798g,
0.1mol) with 200ml concentrated hydrochloric acids, paraformaldehyde (9.009g, 0.3mol) is dissolved in 50ml concentrated hydrochloric acids, constant pressure leakage is added to
In bucket, in the case where nitrogen is protected and is stirred, it is slowly dropped in four-hole boiling flask, after completion of dropping, is warming up to 100 DEG C and continues to react 10
Individual hour；
After reaction terminates, dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is taken to be dissolved in
In 50ml concentrated hydrochloric acids, it is added in constant pressure funnel.In the case where nitrogen is protected and is stirred, it is slowly dropped in four-hole boiling flask, at 100 DEG C
It is lower to continue to react 10 hours, continue logical N2Room temperature is down to, the solvent in reaction bulb is then evaporated, 100ml ethanol is used after cooling
White solid is washed to obtain, 6 hours are dried in vacuo at 60 DEG C, 23.05g products, yield 92.15% is obtained；
Then 8 grams of products are taken, are dissolved in 20 milliliters of distilled water, melamine is added, it is 6 to control solution pH value,
It is warming up to after 80 DEG C of five hours of reaction, suction filtration is washed, drying obtains white solid powder shape macromolecular expansion type flame retardant.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (7)
1. a kind of expansion type flame retardant, it is characterised in that shown in following (1) formula of its structural formula or (2) formula or (3) formula：
Wherein R1For aliphatic chain or fragrant chain；
Wherein R1, R2, R3For aliphatic chain or fragrant chain；
Wherein R1, R2For aliphatic chain or fragrant chain.
2. a kind of preparation method of expansion type flame retardant as claimed in claim 1, it is characterised in that comprise the following steps：
(1) ortho phosphorous acid sodium dihydrogen, organic amine A are dissolved in concentrated hydrochloric acid respectively, will under inert gas importing and magnetic agitation
The hydrochloric acid solution of paraformaldehyde is dissolved with to be slowly dropped in above-mentioned solution, it is anti-in certain temperature and time after completion of dropping
Ying Hou, obtains reaction product B；
(2) concentrated hydrochloric acid solution of dissolving organic amine C and paraformaldehyde is instilled into reaction system, reaction product B is blocked,
After completion of dropping, continue to react certain hour, reaction product D after being blocked, the solvent in cooling, evaporation reaction bulb, cooling
Washed by ethanol, dry, obtain white powder shaped polymer；
(3) the white powder shaped polymer obtained in (2) is dissolved in the aqueous solution containing melamine and neutralized, in
After temperature reaction 2-5 hours, suction filtration is washed, and drying obtains expansion type flame retardant；
The organic amine A is a kind of unary primary amine or binary secondary amine, and the organic amine C is unitary secondary amine.
3. the preparation method of expansion type flame retardant according to claim 2, it is characterised in that in step (1), described time
Sodium dihydrogen phosphite, organic amine A, the mol ratio of paraformaldehyde are 1：1：(2—4).
4. the preparation method of expansion type flame retardant according to claim 2, it is characterised in that described to have in step (2)
The mol ratio of machine amine C and paraformaldehyde is 1：2.
5. the preparation method of expansion type flame retardant according to claim 2, it is characterised in that prepare intermediate reaction product
B and reaction product D reaction temperature are 70-150 DEG C, and the reaction time is 2-12 hours.
6. the preparation method of expansion type flame retardant according to claim 2, it is characterised in that the reaction temperature of neutralization reaction
For 20-100 DEG C, the reaction time of neutralization reaction is 2-5 hours.
7. the preparation method of expansion type flame retardant according to claim 2, it is characterised in that the solution pH value of neutralization reaction
Control is in 4-6.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897129A (en) * | 2014-04-21 | 2014-07-02 | 苏州科技学院相城研究院 | Flame-retardant polymeric MPP compound and preparation method thereof |
| CN103965989A (en) * | 2014-05-06 | 2014-08-06 | 浙江宝晟铁路新材料科技有限公司 | Flame-retarded modifying method for flame-retarded solid lubricating material |
| CN103980541A (en) * | 2014-05-23 | 2014-08-13 | 华东理工大学 | Coating modification method for melamine formaldehyde resin of ammonium polyphosphate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100852384B1 (en) * | 2007-05-15 | 2008-08-14 | 한국화학연구원 | Dendritic nonlinear optical materials based on phosphazene core |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897129A (en) * | 2014-04-21 | 2014-07-02 | 苏州科技学院相城研究院 | Flame-retardant polymeric MPP compound and preparation method thereof |
| CN103965989A (en) * | 2014-05-06 | 2014-08-06 | 浙江宝晟铁路新材料科技有限公司 | Flame-retarded modifying method for flame-retarded solid lubricating material |
| CN103980541A (en) * | 2014-05-23 | 2014-08-13 | 华东理工大学 | Coating modification method for melamine formaldehyde resin of ammonium polyphosphate |
Non-Patent Citations (2)
| Title |
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| "新型含氮阻燃剂的制备及应用研究";苏野;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20100115(第01期);第B016-47页 * |
| "新型氮磷阻燃剂的合成及其阻燃环氧树脂的研究";吴树文;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140715(第07期);第B016-130页 * |
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