CN104327517A - Polymeric phosphate fire retardant and preparation method thereof - Google Patents
Polymeric phosphate fire retardant and preparation method thereof Download PDFInfo
- Publication number
- CN104327517A CN104327517A CN201410580425.4A CN201410580425A CN104327517A CN 104327517 A CN104327517 A CN 104327517A CN 201410580425 A CN201410580425 A CN 201410580425A CN 104327517 A CN104327517 A CN 104327517A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- fire retardant
- preparation
- type phosphate
- aggretion type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a polymeric phosphate fire retardant and relates to a fire retardant and a preparation method thereof. The preparation method of the fire retardant comprises the following steps: firstly, adding hydroquinone to a reactor; secondly, dropwise adding phenylphosphonic dichloride to the reactor in one step, performing a frit reaction at a temperature within the range of 120-260 DEG C for 3-8 hours under the condition of nitrogen protection, cooling until the temperature reaches a room temperature and then heating to perform a reduced pressure reaction for 1-3 hours; and next, blocking the obtained product by use of PEPA to remove halogens, thereby obtaining the polymeric phosphate fire retardant which has a wide application value. The polymeric phosphate fire retardant can be applied to fire retarding of polyolefins and engineering materials. The molecular structure of the polymeric phosphate fire retardant is as shown in the specification.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, particularly relate to a kind of aggretion type phosphate flame retardant and preparation method thereof.
Background technology
Material is that human survival and life must indispensable parts, and being basic substance and the guide of human civilization, is the power directly promoting social development, does not have the development of Materials science, would not have the progress of human society and economic prosperity.Wherein macromolecular material has the incomparable performance of many other materials, in sophisticated technology, national defense construction and national economy every field, become indispensable material.But most of macromolecular material is inflammable, flammable, it is reported the fire occurred in the world in recent decades, wherein major part is relevant with macromolecular material.
For the inflammableness of macromolecular material, finding environmental protection, efficiently fire retardant has become the topic extremely paid close attention in the whole world.Along with synthetic materials plays day by day huge effect in the development of the national economy, stimulate and promoted the fast development of fire retardant technology.Fire retardant is one of important auxiliary agent of polymer modification, and its function makes synthetic materials have flame retardancy, self-extinguishing and smoke elimination.
Therefore, scientific progress and environmental consciousness improve, require that people not only develop the better fire retardant of performance, also more strict requirement proposed to the environmental issue in fire retardant self and use procedure, fire retardant non-halogen, low is poisoned, Composite, press down fuming and become 21 century fire retardant overall development trend.Fire retardant development and application business both domestic and external is adjusting the product structure of fire retardant always, reduces the use of halogenated flame retardant, and increases the development research of the without halide fire retardant to high-efficiency environment friendly.But the kind that can be applied to the halogen-free flame retardants in market is at present also little, and urgently exploitation is suitable for industrialized product innovation.
The fire retardant Applicative time of European and American developed countries is very long, the application of fire retardant is very general, with people environmental protection, safety and healthy in consciousness reinforcement, the developing direction of these fire retardant mature markets turned to the novel environment-friendly fire retardant that exploitation is representative with " without bromination " gradually in the last few years, and all kinds of BACN product constantly emerges.In China, although the fire retardant output of 2008 is at 180,000 ton-22 about ten thousand tons, these fire retardants great majority directly or be indirectly exported to external after roughing, are lessly applied in this country.For plastics, before and after 2012,10% interpolation fire retardant is about had in the plastics of the whole world, and the ratio that current Chinese flame retardant plastics accounts for plastics only has about 2%, lower than world average level, more lower than developed countries and regions such as America and Europes, its reason is not mainly because the domestic flame-retardancy requirements for material also arrives the degree of mandatory execution at present.
Summary of the invention
The object of the present invention is to provide a kind of aggretion type phosphate flame retardant and preparation method thereof, the object of the present invention is to provide a kind of aggretion type phosphate flame retardant and preparation method thereof.Fire retardant prepared by the method improves the not laundry-resistant shortcoming of organophosphate ester flame retardant, not easily moves in the polymer, has excellent weather resistance, preparation method is simple, mild condition, is easy to control, without other additive, the product purity of gained is high, convenient post-treatment.
The object of the invention is to be achieved through the following technical solutions:
A kind of aggretion type phosphate flame retardant, described flame retardant mechanism formula is as follows:
In formula, n is the positive integer of 1 ~ 100.
A kind of aggretion type phosphate flame retardant preparation method, the synthesis step of the method is as follows:
First Resorcinol is joined in reactor, be added in reactor disposable for phosphenyl oxychloride again, react 3 ~ 8h at 120 ~ 260 DEG C after, heat up again after being cooled to room temperature and continue Depressor response 1 ~ 3h, washing, and it is dry, obtain faint yellow solid product, fire retardant will be obtained or midbody compound is placed in reactor, after solubilizing agent dissolves, be warming up to 50 ~ 140 DEG C, add catalyzer, then end-caps PEPA is added in reactor, after reaction 6 ~ 12h, naturally cool to room temperature, finally product is purified, drying can obtain white powdery solids.
Described a kind of aggretion type phosphate flame retardant preparation method, the ratio of described Resorcinol and phosphenyl oxychloride is 1:1 ~ 1:2.0.
Described a kind of aggretion type phosphate flame retardant preparation method, described second step reaction solvent be in methylene dichloride, trichloromethane, acetonitrile, DMF, DMSO, tetrahydrofuran (THF), Isosorbide-5-Nitrae dioxane any one itself or the mixture of arbitrary proportion.
Described a kind of aggretion type phosphate flame retardant preparation method, the solvent that described washing is purified is at least one in methylene dichloride, methyl alcohol, toluene and dimethylbenzene.
Described a kind of aggretion type phosphate flame retardant preparation method, described temperature of reaction is 50 ~ 260 DEG C.
Described a kind of aggretion type phosphate flame retardant preparation method, described end-capping reagent is PEPA; Termination process solvent used is any one or mixed solvent in Isosorbide-5-Nitrae dioxane, DMF, DMSO, methylene dichloride, tetrahydrofuran (THF) or acetonitrile; Product after end-blocking passes through washing, drying treatment.
Described a kind of aggretion type phosphate flame retardant preparation method, the solvent of described washing is any one in Isosorbide-5-Nitrae dioxane, acetonitrile, methyl alcohol, benzene.
Advantage of the present invention and effect are:
Halogen polymeric phosphorus-nitrogen flame retardant is the BACN widely paid close attention to of international flame retardant area in recent years.It has higher phosphorus content and carbon left, has the features such as flame retarding efficiency height and Halogen, low cigarette, low toxicity, hydrolysis, good endurance, meets the requirement that current people preserve the ecological environment, be considered to one of developing direction of current bittern-free flame-proof material.Novel polymeric type phosphate flame retardant is when polymer combustion, by the synergy in acid source, charcoal source, fine and close porous foam layer of charcoal is formed at material surface, this layer of charcoal both can stop the further degraded of internal layer polymer and inflammable gas to the release on surface, again can trap heat to the transmission of polymkeric substance and isolated oxygen source, thus stop spreading and propagating of flame.Compared with traditional halogenated flame retardant, this fire retardant greatly reduces the generation of toxic gas and corrosive gases in combustion, decreases harmful gas purging.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
The first step: to reflux condensing tube, thermometer N are housed
25.506g Resorcinol and 14.637g phosphenyl oxychloride is added in the 100ml there-necked flask of ingress pipe and magneton.Logical N
2protection, is warming up to 160 DEG C and starts reaction, is warming up to 180 DEG C of reaction 3h after 1 hour.Reaction terminates rear logical N
2be warming up to 180 DEG C of Depressor response 1h again after protection is cooled to room temperature, after being down to room temperature for faint yellow solid methylene dichloride dissolve after add separatory after toluene wash mixing, washing, the product after separatory is revolved evaporate to dryness dry, obtains white powdery solids.
Second step: in the 100ml there-necked flask that magnetic agitation, dropping funnel and thermometer are housed, add PEPA3g and 60ml acetonitrile, 4g intermediate is added in dropping funnel, dissolve with 20ml methylene dichloride, after intermediate being dissolved completely with ultrasonic vibration, start to drip intermediate, now keep temperature 75 DEG C, adularescent solid generates, and along with the carrying out of reaction, white solid increases gradually.Drip and terminate follow-up continuous temperature reaction 4 hours; Then be slowly cooled to room temperature, take out solid, with 100ml methylene dichloride and methanol wash, filtration, at 50 DEG C drying gray powdery solid.
Embodiment 2:
The first step: the synthetic method of phosphorous intermediate is with embodiment 1.
Second step:
In the 100ml there-necked flask that magnetic agitation, dropping funnel and thermometer are housed, add PEPA3g, add 0.2g catalyzer and 60ml acetonitrile again, in dropping funnel, add 4g intermediate, dissolve with 20ml methylene dichloride, after intermediate being dissolved completely with ultrasonic vibration, start to drip intermediate, now keep temperature 75 DEG C, adularescent solid generates, along with the carrying out of reaction, white solid increases gradually.Drip and terminate follow-up continuous temperature reaction 4 hours; Then be slowly cooled to room temperature, take out solid, with 100ml methylene dichloride and methanol wash, filtration, at 50 DEG C drying gray powdery solid.
Embodiment 3
The first step: the synthetic method of phosphorous intermediate is with embodiment 1.
In the 100ml there-necked flask that magnetic agitation, dropping funnel and thermometer are housed, add PEPA3g and 60ml acetonitrile, 4g intermediate is added in dropping funnel, dissolve with 20ml tetrahydrofuran (THF), after intermediate being dissolved completely with ultrasonic vibration, start to drip intermediate, now keep temperature 60 C, adularescent solid generates, and along with the carrying out of reaction, white solid increases gradually.Drip and terminate follow-up continuous temperature reaction 4 hours; Then be slowly cooled to room temperature, take out solid, with 100ml methylene dichloride and 20ml methanol wash, filtration, at 50 DEG C drying gray powdery solid.
Embodiment 4
The first step: the synthetic method of phosphorous intermediate is with embodiment 1
In the 250ml there-necked flask that magnetic agitation, dropping funnel and thermometer are housed, add PEPA5g, 0.3g catalyzer and 120ml acetonitrile, add 7.5g intermediate in dropping funnel, dissolves with 20ml methylene dichloride, after intermediate being dissolved completely with ultrasonic vibration, start to drip intermediate, now keep temperature 75 DEG C, adularescent solid generates, along with the carrying out of reaction, white solid increases gradually.Drip and terminate follow-up continuous temperature reaction 4 hours; Then be slowly cooled to room temperature, take out solid, with 100ml methylene dichloride and 20ml methanol wash, filtration, at 50 DEG C drying gray powdery solid.
Claims (8)
1. an aggretion type phosphate flame retardant, is characterized in that, described flame retardant mechanism formula is as follows:
In formula, n is the positive integer of 1 ~ 100.
2. an aggretion type phosphate flame retardant preparation method, is characterized in that, the synthesis step of the method is as follows:
First Resorcinol is joined in reactor, be added in reactor disposable for phosphenyl oxychloride again, react 3 ~ 8h at 120 ~ 260 DEG C after, heat up again after being cooled to room temperature and continue Depressor response 1 ~ 3h, washing, and it is dry, obtain faint yellow solid product, fire retardant will be obtained or midbody compound is placed in reactor, after solubilizing agent dissolves, be warming up to 50 ~ 140 DEG C, add catalyzer, then end-caps PEPA is added in reactor, after reaction 6 ~ 12h, naturally cool to room temperature, finally product is purified, drying can obtain white powdery solids.
3. a kind of aggretion type phosphate flame retardant preparation method according to claim 1, is characterized in that, the ratio of described Resorcinol and phosphenyl oxychloride is 1:1 ~ 1:2.0.
4. a kind of aggretion type phosphate flame retardant preparation method according to claim 1, it is characterized in that, described second step reaction solvent be in methylene dichloride, trichloromethane, acetonitrile, DMF, DMSO, tetrahydrofuran (THF), Isosorbide-5-Nitrae dioxane any one itself or the mixture of arbitrary proportion.
5. a kind of aggretion type phosphate flame retardant preparation method according to claim 1, is characterized in that, the solvent that described washing is purified is at least one in methylene dichloride, methyl alcohol, toluene and dimethylbenzene.
6. a kind of aggretion type phosphate flame retardant preparation method according to claim 1, it is characterized in that, described temperature of reaction is 50 ~ 260 DEG C.
7. a kind of aggretion type phosphate flame retardant preparation method according to claim 1, it is characterized in that, described end-capping reagent is PEPA; Termination process solvent used is any one or mixed solvent in Isosorbide-5-Nitrae dioxane, DMF, DMSO, methylene dichloride, tetrahydrofuran (THF) or acetonitrile; Product after end-blocking passes through washing, drying treatment.
8. a kind of aggretion type phosphate flame retardant preparation method according to claim 7, is characterized in that, the solvent of described washing is any one in Isosorbide-5-Nitrae dioxane, acetonitrile, methyl alcohol, benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410580425.4A CN104327517A (en) | 2014-10-27 | 2014-10-27 | Polymeric phosphate fire retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410580425.4A CN104327517A (en) | 2014-10-27 | 2014-10-27 | Polymeric phosphate fire retardant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104327517A true CN104327517A (en) | 2015-02-04 |
Family
ID=52402328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410580425.4A Pending CN104327517A (en) | 2014-10-27 | 2014-10-27 | Polymeric phosphate fire retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104327517A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662332A (en) * | 2020-06-02 | 2020-09-15 | 桂林理工大学 | Organophosphorus flame retardant with active amino groups and preparation method and application thereof |
| CN113956485A (en) * | 2021-11-18 | 2022-01-21 | 山东艾科高分子材料有限公司 | Preparation method of modified polyphosphate flame retardant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328269A (en) * | 2008-07-20 | 2008-12-24 | 大连理工大学 | Preparation of polyphosphate flame retardant having dicyclic phosphoric acid ester structure |
| US20110218260A1 (en) * | 2008-10-21 | 2011-09-08 | Albemarle Corporation | Mixed Glycol Polyphosphonate Compounds |
| CN102627772A (en) * | 2012-04-12 | 2012-08-08 | 南京师范大学 | Method for synthesizing polymerized phenyl phosphonate by performing solid-liquid two-phase reaction |
| CN102775442A (en) * | 2012-07-11 | 2012-11-14 | 合肥安聚达新材料科技有限公司 | Oligomer phosphonate and preparation method and application thereof |
-
2014
- 2014-10-27 CN CN201410580425.4A patent/CN104327517A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328269A (en) * | 2008-07-20 | 2008-12-24 | 大连理工大学 | Preparation of polyphosphate flame retardant having dicyclic phosphoric acid ester structure |
| US20110218260A1 (en) * | 2008-10-21 | 2011-09-08 | Albemarle Corporation | Mixed Glycol Polyphosphonate Compounds |
| CN102627772A (en) * | 2012-04-12 | 2012-08-08 | 南京师范大学 | Method for synthesizing polymerized phenyl phosphonate by performing solid-liquid two-phase reaction |
| CN102775442A (en) * | 2012-07-11 | 2012-11-14 | 合肥安聚达新材料科技有限公司 | Oligomer phosphonate and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HUA-QIAO PENG等: "A novel charring agent containing caged bicyclic phosphate and its application in intumescent flame retardant polypropylene systems", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662332A (en) * | 2020-06-02 | 2020-09-15 | 桂林理工大学 | Organophosphorus flame retardant with active amino groups and preparation method and application thereof |
| CN111662332B (en) * | 2020-06-02 | 2023-10-13 | 桂林理工大学 | Organophosphorus flame retardant with active amino groups, and preparation method and application thereof |
| CN113956485A (en) * | 2021-11-18 | 2022-01-21 | 山东艾科高分子材料有限公司 | Preparation method of modified polyphosphate flame retardant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | A bio-based ionic complex with different oxidation states of phosphorus for reducing flammability and smoke release of epoxy resins | |
| CN105175735B (en) | A kind of branched Phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN104844804A (en) | Polymer type phosphorus-nitrogen intumescent flame retardant and preparation method therefor | |
| Chen et al. | Combustion and thermal degradation properties of flame-retardant TPU based on EMIMPF 6 | |
| CN102827373B (en) | Preparation method of phosphorus-nitrogen intumescent flame retardant | |
| CN102250384A (en) | Preparation and application of flame retardant | |
| CN108794525A (en) | A kind of preparation method of phosphonium flame retardant | |
| CN115286726B (en) | Flame retardant modifier for plastics and preparation method thereof | |
| CN104327517A (en) | Polymeric phosphate fire retardant and preparation method thereof | |
| CN104403106A (en) | Polymeric phosphorus nitrogen expansion type flame retardant agent and preparation method thereof | |
| CN109836938B (en) | Preparation method of silicon-containing halogen-free intumescent phosphazene fire retardant coating | |
| CN103102483A (en) | Higher molecular weight type intumescent flame retardant containing triazine structure and synthetic method thereof | |
| CN104311818B (en) | A kind of phosphorous, nitrogen aggretion type fire retardant and preparation method thereof | |
| CN101570518A (en) | Preparation method for expansion type melamine hypophosphite fire retardant | |
| CN104478935A (en) | Preparation method of nitrophenoxy cyclotriphosphazene flame retardant | |
| CN103113620A (en) | Phosphine-oxide flame retardant and preparation method thereof | |
| CN114957655B (en) | Phosphorus-nitrogen high-molecular flame retardant and preparation method thereof | |
| CN106045928A (en) | Method for preparing triazine ring carbon-forming agent containing polyhydroxyl | |
| CN103387591B (en) | A kind of phosphorous dibasic alcohol and preparation method thereof | |
| CN104530430A (en) | High-tenacity flame-retardant bismaleimide resin and preparation method thereof | |
| CN102604157B (en) | Flame retardant and preparation method thereof | |
| CN104261396A (en) | Preparation method of expansible graphite with flame retardant property | |
| JP5936375B2 (en) | Flame retardant composition and polycarbonate resin composition | |
| CN105061809A (en) | Solid organic phosphate flame retardant and preparation method thereof | |
| CN104926880B (en) | The preparation method of fire retardant trihydroxy methyl phosphine oxide caged bi-ester of phosphite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150204 |
|
| RJ01 | Rejection of invention patent application after publication |