CN104927060A - Intumescent flame retardant and preparation method thereof - Google Patents
Intumescent flame retardant and preparation method thereof Download PDFInfo
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- CN104927060A CN104927060A CN201510066669.5A CN201510066669A CN104927060A CN 104927060 A CN104927060 A CN 104927060A CN 201510066669 A CN201510066669 A CN 201510066669A CN 104927060 A CN104927060 A CN 104927060A
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Abstract
The invention provides an intumescent flame retardant and a preparation method thereof. The method comprises the following steps: (1) sodium dihydrogen hypophosphite and organic amine A are respectively dissolved in concentrated hydrochloric acid; under inert gas introduction and magnetic stirring, a paraformaldehyde solution is slowly dropped into the above solution; when dropping is finished, a reaction is carried out for a certain period of time under a certain temperature, such that a reaction product B is obtained; (2) a concentrated hydrochloric acid solution with dissolved organic amine C and paraformaldehyde is dropped into the reaction system, such that the reaction product B is capped; when dropping is finished, a reaction is continued for 2-12h, such that a capped reaction product D is obtained; cooling, organic solvent extraction, filtering, washing, and drying are carried out, such that a white powdery polymer is obtained; and (3) the white powdery polymer obtained in the step (2) is dissolved in a water solution comprising melamine for neutralization; a neutralization and heating reaction is carried out for 2-5h; and suction filtration, washing and drying are carried out, such that the intumescent flame retardant is obtained. The flame retardant and the preparation method have the advantages of simple process and high yield.
Description
Technical field
The present invention relates to technical field of flame retardant, particularly relate to a kind of expansion type flame retardant and preparation method thereof.
Background technology
Along with the flourish of macromolecular material brings many facilities to the life of people, people enjoy that polymer science and technology brings simultaneously easily, also subject the great disaster brought because of the inflammableness of macromolecular material, therefore improving the flame-retarded technology level of macromolecular material, is one of focus that current scientific and technological circle are studied.In macromolecular material, introduce fire retardant, the fire hazard of material can be reduced.Traditional small molecules fire retardant, due to easy to process and be used widely, but to there is flame retarding efficiency low for small molecules fire retardant, and addition is large, poor with material compatibility, affects the shortcoming of the performances such as the machinery of material, electricity, makes it apply and be restricted.The macromolecular fire retardant of recent domestic research synthesis, because its consistency with material is better, affects less on the physicals of material, and receives much concern.
Summary of the invention
The object of the present invention is to provide a kind of macromole expansion type flame retardant and preparation method thereof, by improving the consistency of fire retardant and macromolecular material and utilizing the synergistic fire retardation between multiple ignition-proof element to improve the flame retardant properties of polymkeric substance, solve this kind of compound as flame-retardant additive in multiple polymers.
A kind of expansion type flame retardant, shown in following 1 formula of its structural formula or 2 formulas or 3 formulas:
Wherein R
1for aliphatic chain or fragrant chain;
Wherein R
1, R
2, R
3for aliphatic chain or fragrant chain;
Wherein R
1, R
2for aliphatic chain or fragrant chain.
A preparation method for expansion type flame retardant, comprises the following steps:
(1) ortho phosphorous acid sodium dihydrogen, organic amine A are dissolved in concentrated hydrochloric acid respectively, import at rare gas element and under magnetic agitation, the hydrochloric acid soln being dissolved with paraformaldehyde be slowly added drop-wise in above-mentioned solution, after dropwising, after certain temperature and the reaction of time, obtain reaction product B;
(2), in reaction system, the concentrated hydrochloric acid solution of organic amine C and paraformaldehyde is dissolved in instillation, end-blocking is carried out to reaction product B, after dropwising, continue certain hour of reaction, obtain reaction product D after end-blocking, the solvent in cooling, evaporation reaction flask, through washing with alcohol after cooling, dry, obtain white powder shaped polymer;
(3) by the white powder polymer dissolution obtained in (2) in containing trimeric cyanamide the aqueous solution in neutralize, in and after temperature reaction 2-5 hour, suction filtration, washing, dry, obtain expansion type flame retardant.
Further, the preparation method of expansion type flame retardant as above, in step 1, the mol ratio of described ortho phosphorous acid sodium dihydrogen, organic amine A, paraformaldehyde is 1:1:(2-4).
Further, the preparation method of expansion type flame retardant as above, in step 2, the mol ratio of described organic amine C and paraformaldehyde is 1:2.
Further, the preparation method of expansion type flame retardant as above, the temperature of reaction of preparation intermediate reaction product B and reaction product D is 70-150 DEG C, and the reaction times is 2-12 hour.
Further, the preparation method of expansion type flame retardant as above, the temperature of reaction of neutralization reaction is 20-100 DEG C, and the reaction times of neutralization reaction is 2-5 hour.
Further, the preparation method of expansion type flame retardant as above, the solution pH value of neutralization reaction controls at 4-6.
Further, the preparation method of expansion type flame retardant as above, described organic amine A is a kind of unary primary amine or binary secondary amine.
Further, the preparation method of expansion type flame retardant as above, described organic amine C is unitary secondary amine.
Expansion type flame retardant provided by the invention can be used in multiple polymers, to improve the flame retardant properties of polymkeric substance.Present invention process working condition is simple, productive rate is higher, last handling process is easy.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below technical scheme in the present invention be clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Expansion type flame retardant preparation method provided by the invention is: first by organic amine A, ortho phosphorous acid sodium dihydrogen and paraformaldehyde Reactive Synthesis outgoing-line type polymer B in concentrated hydrochloric acid, wherein, the mol ratio of organic amine A, ortho phosphorous acid sodium dihydrogen and paraformaldehyde is 1:1:(2-4), under this proportioning, side reaction is few, product purity is high, and too high or too low proportioning all will make product purity decline.Then with organic amine C and paraformaldehyde, end-blocking is carried out to B and synthesize D; Finally obtain a kind of macromole expansion type flame retardant with in trimeric cyanamide with D.Raw material organic amine A is the mixture of common a kind of unary primary amine or binary secondary amine or more than one unary primary amine or binary secondary amine arbitrary proportion, and organic amine C is a kind of unitary secondary amine.The temperature of reaction of synthesizing polymer B and D in preparation process is preferably 70-150 DEG C, and the reaction times is preferably 2-12 hours.The temperature of reaction of neutralization reaction is preferably 20-100 DEG C, and the reaction times is preferably 2-5 hours, and the solution pH value of neutralization reaction is preferably 4-6, pH value is too high or too lowly side reaction all will be made to increase, product purity declines, and therefore, pH value controls at 4-6 by the present invention.
The preparation method of described a kind of macromole expansion type flame retardant, the consumption of solvent concentrated hydrochloric acid described in it is 10-100 times of ortho phosphorous acid sodium dihydrogen consumption.
Embodiment 1:
Piperazine (8.614g is added in the 500ml four-hole boiling flask that thermometer, nitrogen importing, 100ml constant pressure funnel, magneton and reflux condensing tube and device for absorbing tail gas be housed, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) with 200ml concentrated hydrochloric acid, under nitrogen protection and magnetic agitation, paraformaldehyde (9.009g will be dissolved with, 50ml concentrated hydrochloric acid 0.3mol), join in constant pressure funnel, slowly be added drop-wise in four-hole boiling flask, after dropwising, be warmed up to 70 DEG C and continue reaction 12 hours;
After reaction terminates, get dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is dissolved in 50ml concentrated hydrochloric acid, join in constant pressure funnel.Under nitrogen protection and magnetic agitation, be slowly added drop-wise in four-hole boiling flask, at 100 DEG C, continue reaction 5 hours, continue logical N
2be down to room temperature, then evaporate the solvent in reaction flask, obtain white solid by 100ml washing with alcohol after cooling, vacuum-drying 6 hours at 60 DEG C, obtains 19.63g product, productive rate 89%;
Then get 8 grams of products, be dissolved in 20 ml distilled waters containing trimeric cyanamide, controlling solution pH value is 4, and be warmed up to 80 DEG C of reactions after 5 hours, suction filtration, washing, dries, obtain white solid powder shape macromole expansion type flame retardant.
Embodiment 2:
Homopiperazine (10.218g is added in the 500ml four-hole boiling flask that thermometer, nitrogen importing, 100ml constant pressure funnel, magneton and reflux condensing tube and device for absorbing tail gas be housed, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) with 200ml concentrated hydrochloric acid, under nitrogen protection and magnetic agitation, paraformaldehyde (6.006g will be dissolved with, 50ml concentrated hydrochloric acid 0.2mol), join in constant pressure funnel, slowly be added drop-wise in four-hole boiling flask, after dropwising, be warmed up to 150 DEG C and continue reaction 2 hours;
After reaction terminates; get dimethylamine (0.4508g; 0.01mol) with paraformaldehyde (0.601g; 0.02mol) be dissolved in 50ml concentrated hydrochloric acid; join in constant pressure funnel, under nitrogen protection and magnetic agitation, be slowly added drop-wise in four-hole boiling flask; at 150 DEG C, continue reaction 5 hours, continue logical N
2be down to room temperature, then evaporate the solvent in reaction flask, obtain white solid by 100ml washing with alcohol after cooling, vacuum-drying 6 hours at 60 DEG C, obtains 22.03g product, productive rate 92%;
Then get 8 grams of products, be dissolved in 20 ml distilled waters, add trimeric cyanamide, controlling solution pH value is 6, and be warmed up to 100 DEG C of reactions after 5 hours, suction filtration, washing, dries, obtain white solid powder shape macromole expansion type flame retardant.
Embodiment 3:
Methylamine (3.106g is added in the 500ml four-hole boiling flask that thermometer, nitrogen importing, 100ml constant pressure funnel, magneton and reflux condensing tube and device for absorbing tail gas be housed, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) with 200ml concentrated hydrochloric acid, under nitrogen protection and magnetic agitation, paraformaldehyde (12.012g will be dissolved with, 50ml concentrated hydrochloric acid 0.4mol), join in constant pressure funnel, slowly be added drop-wise in four-hole boiling flask, after dropwising, be warmed up to 100 DEG C and continue reaction 12 hours;
After reaction terminates, get dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is dissolved in 50ml concentrated hydrochloric acid, join in constant pressure funnel.Under nitrogen protection and magnetic agitation, be slowly added drop-wise in four-hole boiling flask, at 100 DEG C, continue reaction 10 hours, continue logical N
2be down to room temperature, then evaporate the solvent in reaction flask, obtain white solid by 100ml washing with alcohol after cooling, vacuum-drying 6 hours at 60 DEG C, obtains 15.23g product, productive rate 92.3%;
Then get 8 grams of products, be dissolved in 20 ml distilled waters, add trimeric cyanamide, controlling solution pH value is 5, and be warmed up to 80 DEG C of reactions after 5 hours, suction filtration, washing, dries, obtain white solid powder shape macromole expansion type flame retardant.
Embodiment 4:
Cyclohexylmethylamine (11.320g is added in the 500ml four-hole boiling flask that thermometer, nitrogen importing, 100ml constant pressure funnel, magneton and reflux condensing tube and device for absorbing tail gas be housed, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) with 200ml concentrated hydrochloric acid, under nitrogen protection and magnetic agitation, paraformaldehyde (9.009g will be dissolved with, 50ml concentrated hydrochloric acid 0.3mol), join in constant pressure funnel, slowly be added drop-wise in four-hole boiling flask, after dropwising, be warmed up to 100 DEG C and continue reaction 10 hours;
After reaction terminates; get dimethylamine (0.4508g; 0.01mol) with paraformaldehyde (0.601g; 0.02mol) be dissolved in 50ml concentrated hydrochloric acid; join in constant pressure funnel, under nitrogen protection and magnetic agitation, be slowly added drop-wise in four-hole boiling flask; at 100 DEG C, continue reaction 10 hours, continue logical N
2be down to room temperature, then evaporate the solvent in reaction flask, obtain white solid by 100ml washing with alcohol after cooling, vacuum-drying 6 hours at 60 DEG C, obtains 21.28g product, productive rate 84.32%;
Then get 8 grams of products, be dissolved in 20 ml distilled waters, add trimeric cyanamide, controlling solution pH value is 6, and be warmed up to 80 DEG C of reactions after 5 hours, suction filtration, washing, dries, obtain white solid powder shape macromole expansion type flame retardant.
Embodiment 5:
Benzene methanamine (10.816g is added in the 500ml four-hole boiling flask that thermometer, nitrogen importing, 100ml constant pressure funnel, magneton and reflux condensing tube and device for absorbing tail gas be housed, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) with 200ml concentrated hydrochloric acid, under nitrogen protection and magnetic agitation, paraformaldehyde (9.009g will be dissolved with, 50ml concentrated hydrochloric acid 0.3mol), join in constant pressure funnel, slowly be added drop-wise in four-hole boiling flask, after dropwising, be warmed up to 100 DEG C and continue reaction 10 hours;
After reaction terminates, get dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is dissolved in 50ml concentrated hydrochloric acid, join in constant pressure funnel.Under nitrogen protection and magnetic agitation, be slowly added drop-wise in four-hole boiling flask, at 100 DEG C, continue reaction 10 hours, continue logical N
2be down to room temperature, then evaporate the solvent in reaction flask, obtain white solid by 100ml washing with alcohol after cooling, vacuum-drying 6 hours at 60 DEG C, obtains 20.05g product, productive rate 82.85%;
Then get 8 grams of products, be dissolved in 20 ml distilled waters, add trimeric cyanamide, controlling solution pH value is 6, and be warmed up to 80 DEG C of reactions after 5 hours, suction filtration, washing, dries, obtain white solid powder shape macromole expansion type flame retardant.
Embodiment 6:
Diethyl ethylenediamine (11.620g is added in the 500ml four-hole boiling flask that thermometer, nitrogen importing, 100ml constant pressure funnel, magneton and reflux condensing tube and device for absorbing tail gas be housed, 0.1mol), ortho phosphorous acid sodium dihydrogen (8.798g, 0.1mol) with 200ml concentrated hydrochloric acid, by paraformaldehyde (9.009g, 0.3mol) be dissolved in 50ml concentrated hydrochloric acid, join in constant pressure funnel, in nitrogen protection with under stirring, slowly be added drop-wise in four-hole boiling flask, after dropwising, be warmed up to 100 DEG C and continue reaction 10 hours;
After reaction terminates, get dimethylamine (0.4508g, 0.01mol) and paraformaldehyde (0.601g, 0.02mol) is dissolved in 50ml concentrated hydrochloric acid, join in constant pressure funnel.In nitrogen protection with under stirring, be slowly added drop-wise in four-hole boiling flask, at 100 DEG C, continue reaction 10 hours, continue logical N
2be down to room temperature, then evaporate the solvent in reaction flask, obtain white solid by 100ml washing with alcohol after cooling, vacuum-drying 6 hours at 60 DEG C, obtains 23.05g product, productive rate 92.15%;
Then get 8 grams of products, be dissolved in 20 ml distilled waters, add trimeric cyanamide, controlling solution pH value is 6, and be warmed up to 80 DEG C of reactions after five hours, suction filtration, washing, dries, obtain white solid powder shape macromole expansion type flame retardant.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (9)
1. an expansion type flame retardant, is characterized in that, shown in following 1 formula of its structural formula or 2 formulas or 3 formulas:
Wherein R
1for aliphatic chain or fragrant chain;
Wherein R
1, R
2, R
3for aliphatic chain or fragrant chain;
Wherein R
1, R
2for aliphatic chain or fragrant chain.
2. a preparation method for expansion type flame retardant, is characterized in that, comprises the following steps:
(1) ortho phosphorous acid sodium dihydrogen, organic amine A are dissolved in concentrated hydrochloric acid respectively, import at rare gas element and under magnetic agitation, the hydrochloric acid soln being dissolved with paraformaldehyde be slowly added drop-wise in above-mentioned solution, after dropwising, after certain temperature and the reaction of time, obtain reaction product B;
(2), in reaction system, the concentrated hydrochloric acid solution of organic amine C and paraformaldehyde is dissolved in instillation, end-blocking is carried out to reaction product B, after dropwising, continue certain hour of reaction, obtain reaction product D after end-blocking, the solvent in cooling, evaporation reaction flask, through washing with alcohol after cooling, dry, obtain white powder shaped polymer;
(3) by the white powder polymer dissolution obtained in (2) in containing trimeric cyanamide the aqueous solution in neutralize, in and after temperature reaction 2-5 hour, suction filtration, washing, dry, obtain expansion type flame retardant.
3. the preparation method of expansion type flame retardant according to claim 2, is characterized in that, in step 1, the mol ratio of described ortho phosphorous acid sodium dihydrogen, organic amine A, paraformaldehyde is 1:1:(2-4).
4. the preparation method of expansion type flame retardant according to claim 2, is characterized in that, in step 2, the mol ratio of described organic amine C and paraformaldehyde is 1:2.
5. the preparation method of expansion type flame retardant according to claim 2, is characterized in that, the temperature of reaction of preparation intermediate reaction product B and reaction product D is 70-150 DEG C, and the reaction times is 2-12 hour.
6. the preparation method of expansion type flame retardant according to claim 2, is characterized in that, the temperature of reaction of neutralization reaction is 20-100 DEG C, and the reaction times of neutralization reaction is 2-5 hour.
7. the preparation method of expansion type flame retardant according to claim 2, is characterized in that, the solution pH value of neutralization reaction controls at 4-6.
8. the preparation method of expansion type flame retardant according to claim 2, is characterized in that, described organic amine A is a kind of unary primary amine or binary secondary amine.
9. the preparation method of expansion type flame retardant according to claim 1, is characterized in that, described organic amine C is unitary secondary amine.
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Citations (4)
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| KR100852384B1 (en) * | 2007-05-15 | 2008-08-14 | 한국화학연구원 | Dendritic nonlinear optical materials based on phosphazene core |
| 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 |
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Patent Citations (4)
| 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 |
| 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 |
|---|
| 吴树文: ""新型氮磷阻燃剂的合成及其阻燃环氧树脂的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 苏野: ""新型含氮阻燃剂的制备及应用研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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