CN102952290A - Preparation method of novel synergistic intumescent flame retardant - Google Patents
Preparation method of novel synergistic intumescent flame retardant Download PDFInfo
- Publication number
- CN102952290A CN102952290A CN2012103744955A CN201210374495A CN102952290A CN 102952290 A CN102952290 A CN 102952290A CN 2012103744955 A CN2012103744955 A CN 2012103744955A CN 201210374495 A CN201210374495 A CN 201210374495A CN 102952290 A CN102952290 A CN 102952290A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- preparation
- expansion type
- type flame
- novel synergistic
- 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.)
- Granted
Links
Abstract
The invention provides a preparation method of a novel synergistic intumescent flame retardant, wherein 2,4,6-tri(2,4-dihydroxyphenyl)-1,3-5-triazine and cyclic phosphate ester are used as raw materials. The preparation method provided by the invention is simple in technique, the reaction process is liable to control, the thermal stability of the synthesized flame retardant is good, the char yield is high, and the flame retardant efficiency is high.
Description
Technical field
The invention belongs to flame retardant area, be specifically related to the preparation method of novel synergistic expansion type flame retardant.
Background technology
Present typical Intumscent Flame Retardant System such as ammonium polyphosphate (APP)/tetramethylolmethane (PER)/trimeric cyanamide (MEL) is acid source, carbon source and source of the gas multicomponent mixture, because it is many to add component, between each component and the consistency between component and matrix have certain drawback, and then affect Flame Retardancy energy and physical and mechanical properties.The research and development of scientific experiment proof integrate the unit molecule expansion type flame retardant (IFR) of carbon source, acid source, source of the gas, realize that " three sources " effect functional group brings into play expandable flame retardant effect and effect in the single component molecule, can effectively solve fire retardant and macromolecular material compatibility problem, avoid compound IFR in polymkeric substance, to move, reduce the fire retardant addition, significant to improving flame-retardant polymer usefulness.And the expanding fire retardant flame retardant effect that contains triazine structural units is remarkable, can give by the electrical property of ignition resistant substrate excellence, mechanical property, splendid thermostability, and have low toxicity, the advantage such as cheap.
Summary of the invention
The present invention is in order to solve the prior art existing problems, adopt 2,4,6-three (2,4-dihydroxy phenyl)-1,3,5-triazine and annular phosphate are as starting raw material of the present invention, and providing two kinds of novel unit molecule expansion type flame retardants is fire retardant 2,4,6-three (2,4-two (5,5-dimethyl-1, the assorted own interior phosphorus acyloxy of 3-dioxy ring) phenyl)-1,3,5-triazine (TDDMDOBT) and fire retardant 2,4,6-three (2,4-two (5,5-dibromo methyl isophthalic acid, the assorted own interior phosphorus acyloxy of 3-dioxy ring) phenyl)-1,3,5-triazine (TDDBDOBT) is applicable to polypropylene, polyethylene, Resins, epoxy, the inflammable macromolecular material such as polyurethane foam flame-retardant modified.
It is as follows to the invention provides two kinds of novel dendritic unit molecule P-N and P-N-Br synergistic expansion type flame retardant TDDMDOBT and TDDBDOBT(structural formula) the preparation method, these two kinds of fire retardants are with 2,4,6 three (2, the 4-dihydroxy phenyl)-1,3,5-triazines and annular phosphate be as raw material.Technique of the present invention is simple, and reaction process is convenient to control, synthetic fire retardant good thermal stability, and charring rate is high, and flame retarding efficiency is high.
Fire retardant TDDMDOBT fire retardant TDDBDOBT
The present invention proposes two kinds of novel unit molecule P-N and P-N-Br synergistic expansion type flame retardant TDDMDOBT and TDDBDOBT, can prepare according to following technology:
Fire retardant TDDMDOBT preferably synthetic method is: the nucleophilic addition(Adn) substitution reaction occurs in the material and the annular phosphate that contain the poly-hydroxy triazine structural units in polar solvent, making fire retardant TDDMDOBT of the present invention is 2,4,6-three (2,4-two (5,5-dimethyl-1, the assorted own interior phosphorus acyloxy of 3-dioxy ring) phenyl)-1,3,5-triazine.
Final reacting product can separate with classical method.Method is solvent to be steamed remove preferably, gets light yellow solid, adds ethanol in reaction flask, behind dissolution of solid, steaming desolventizes again, and the faint yellow solid that is slightly turned white adds distilled water curing in reaction flask, filter, get white product, with ethyl alcohol recrystallization twice, make product.
According to the technology of preparing that the invention provides novel unit molecule P-N synergistic expansion type flame retardant TDDMDOBT, the product that makes has good thermostability and becomes charcoal, and molecular weight is 1293.7, and heat decomposition temperature is 257 ℃ under the nitrogen atmosphere, neat coal amout is 55.64%, and phosphorus content is 14.38%.
Fire retardant TDDBDOBT preferably synthetic method is: the material and the bromination annular phosphate that contain the poly-hydroxy triazine structural units, the nucleophilic addition(Adn) substitution reaction occurs in polar solvent, making fire retardant TDDBDOBT of the present invention is 2, (2,4-two (5 for 4,6-three, 5-dibromo methyl isophthalic acid, the assorted own interior phosphorus acyloxy of 3-dioxy ring) phenyl)-1,3,5 triazines.
Final reacting product can separate with classical method.Method is solvent to be steamed remove preferably, gets light yellow solid, adds ethyl acetate in reaction flask, behind dissolution of solid, steaming desolventizes again, and the faint yellow solid that is slightly turned white adds distilled water curing in reaction flask, filter, get white product, with ethyl alcohol recrystallization twice, make product.
According to the technology of preparing that the invention provides novel unit molecule P-N-Br synergistic expansion type flame retardant TDDBDOBT, the product that makes has good thermostability and becomes charcoal, molecular weight is 2240.6, heat decomposition temperature is 334.55 ℃ under the nitrogen atmosphere, neat coal amout is 47.94%, phosphorus content is 8.30%, and bromine content is 42.31%.
Embodiment
Following instance further specifies the preparation process of the preparation novel unit molecule P-N of the present invention and P-N-Br synergistic expansion type flame retardant TDDMDOBT and TDDBDOBT, but these examples be not interpreted as limitation of the present invention in all senses.
The preparation of embodiment 1, TDDMDOBT
In 500mL four-hole round-bottomed flask, add 2,4,6-three (2, the 4-dihydroxy phenyl)-and 1,3,5-triazines 19.0g, 5,5-dimethyl-1,3-dioxaphosphorinane phosphoryl chloride 73.6g, acetonitrile 300mL, stirring mixes it and fully dissolving, and it is light yellow that solution colour is.Solution colour is deepened during the reaction beginning, and a large amount of white smoke occur in the reaction flask, and solution colour is tending towards light yellow gradually subsequently, and heating continues reaction 24h, and it is suspension liquid that solution presents ivory buff, stopped reaction.The solvent steaming is removed, get light yellow solid, in reaction flask, add ethanol 300mL, behind dissolution of solid, steaming desolventizes again, and the faint yellow solid that is slightly turned white adds distilled water curing in reaction flask, filter, get white product,, getting the white solid powdered compounds is fire retardant TDDMDOBT sterling 55.0g, productive rate 90.5%, m.p.143 ~ 145 ℃.
The preparation of embodiment 2, TDDBDOBT
In 500mL four-hole round-bottomed flask, add 2,4,6-three (2, the 4-dihydroxy phenyl)-and 1,3,5-triazines 10.5g, 5,5-dibromo methyl isophthalic acid, 3-dioxaphosphorinane phosphoryl chloride 65.8g, acetonitrile 500mL, stirring mixes it and fully dissolving, and it is light yellow that solution colour is.After heating continues reaction 6h, stopped reaction.With solvent steam remove after, in reaction flask, add ethyl acetate 300mL, behind dissolution of solid, again steam and desolventize, obtain white solid, filter, getting the white solid powdered compounds is fire retardant TDDBDOBT sterling 53.7g, productive rate 92.3%, m.p.133 ~ 135 ℃.
Claims (7)
1. the preparation method of a novel synergistic expansion type flame retardant, it is characterized in that: the material and the annular phosphate that contain the poly-hydroxy triazine structural units are synthesis material, and the poly-hydroxy triazine structural units is 2,4,6-three (2,4-dihydroxy phenyl)-1,3,5-triazine and annular phosphate generation nucleophilic addition(Adn) substitution reaction make fire retardant 2, (2,4-two (5 for 4,6-three, 5-dimethyl-1, the assorted own interior phosphorus acyloxy of 3-dioxy ring) phenyl)-1,3,5-triazines.
2. the preparation method of a kind of novel synergistic expansion type flame retardant as claimed in claim 1, it is characterized in that: described annular phosphate is the bromination annular phosphate.
3. the preparation method of a kind of novel synergistic expansion type flame retardant as claimed in claim 2, it is characterized in that: the material and the bromination annular phosphate that contain the poly-hydroxy triazine structural units are synthesis material, the poly-hydroxy triazine structural units is 2,4,6-three (2, the 4-dihydroxy phenyl)-1,3,5-triazines and bromination annular phosphate generation nucleophilic addition(Adn) substitution reaction, make fire retardant 2, (2,4-two (5 for 4,6-three, 5-dibromo methyl isophthalic acid, the assorted own interior phosphorus acyloxy of 3-dioxy ring) phenyl)-1,3,5-triazines.
4. the preparation method of a kind of novel synergistic expansion type flame retardant as claimed in claim 1, it is characterized in that: described annular phosphate is 5,5-dimethyl-1,3-dioxaphosphorinane phosphoryl chloride.
5. a kind of preparation method of novel synergistic expansion type flame retardant as claimed in claim 2 or claim 3, it is characterized in that: described bromination annular phosphate is 5,5-dibromo methyl isophthalic acid, 3-dioxaphosphorinane phosphoryl chloride.
6. the preparation method of a kind of novel synergistic expansion type flame retardant according to claim 4 is characterized in that: add 2,4 in reaction vessel, 6-three (2, the 4-dihydroxy phenyl)-1,3,5-triazines 19.0g and 5,5-dimethyl-1,3-dioxaphosphorinane phosphoryl chloride 73.6g makes its abundant stirring and dissolving in the 300mL anhydrous acetonitrile, reacting by heating 20～24h, until solution is when presenting the ivory buff suspension liquid, stopped reaction; The solvent steaming is removed, get light yellow solid, in reaction vessel, add the 300mL dehydrated alcohol, behind dissolution of solid, steaming desolventizes the faint yellow solid that is slightly turned white again, add distilled water in the reaction vessel and solidify, filter, get white product, be 2,4,6-three (2,4-two (5,5-dimethyl-1, the assorted own interior phosphorus acyloxy of 3-dioxy ring) phenyl)-1,3,5-triazine.
7. the preparation method of a kind of novel synergistic expansion type flame retardant according to claim 5, it is characterized in that: in reaction vessel, add 2,4,6-three (2, the 4-dihydroxy phenyl)-1,3,5-triazine 10.5g and 5,5-dibromo methyl isophthalic acid, 3-dioxaphosphorinane phosphoryl chloride 65.8g, make its abundant stirring and dissolving in the 500mL anhydrous acetonitrile, reacting by heating 5～6h, stopped reaction; Solvent steamed removes, add in the reaction vessel 300ml ethyl acetate with dissolution of solid after, again steam and desolventize, get the white solid powdered compounds, namely 2,4, (2,4-two (5 for 6-three, 5-dibromo methyl isophthalic acid, the assorted own interior phosphorus acyloxy of 3-dioxy ring) phenyl)-1,3,5-triazines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210374495.5A CN102952290B (en) | 2012-09-29 | 2012-09-29 | The preparation method of synergistic intumescent flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210374495.5A CN102952290B (en) | 2012-09-29 | 2012-09-29 | The preparation method of synergistic intumescent flame retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102952290A true CN102952290A (en) | 2013-03-06 |
| CN102952290B CN102952290B (en) | 2017-10-13 |
Family
ID=47761718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210374495.5A Active CN102952290B (en) | 2012-09-29 | 2012-09-29 | The preparation method of synergistic intumescent flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102952290B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854294A (en) * | 2017-01-05 | 2017-06-16 | 江南大学 | A kind of annular phosphate flame retardant and preparation method thereof |
| WO2018161619A1 (en) * | 2017-03-07 | 2018-09-13 | 山东省化工研究院 | Triazine compound, preparation method therefor, and application thereof |
-
2012
- 2012-09-29 CN CN201210374495.5A patent/CN102952290B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| 冯亚青等: "《助剂化学及工艺学》", 30 June 1997, 化学工业出版社 * |
| 卢林刚等: "新型树状单分子磷-氮膨胀阻燃剂的合成及阻燃性能的研究", 《化学学报》 * |
| 卢林刚等: "新型树状磷-溴协效阻燃剂1,3,5-三（5,5-二溴甲基-1,3-二氧杂己内磷酰氧基）苯的合成及其引用研究", 《化学试剂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854294A (en) * | 2017-01-05 | 2017-06-16 | 江南大学 | A kind of annular phosphate flame retardant and preparation method thereof |
| WO2018161619A1 (en) * | 2017-03-07 | 2018-09-13 | 山东省化工研究院 | Triazine compound, preparation method therefor, and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102952290B (en) | 2017-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102757579B (en) | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof | |
| CN103113619B (en) | Triazine ring containing caged organic phosphate flame retardant and preparation method thereof | |
| CN103275129B (en) | A kind of preparation method of Caged Bicyclic Phosphate Flame Retardants | |
| CN104371116A (en) | Preparation method and application of lignin-based intumescent flame retardant | |
| CN105440308A (en) | High phosphorus-nitrogen content flame retardant and preparation method thereof | |
| CN105924645A (en) | Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant | |
| CN106496570B (en) | A kind of phosphorus-nitrogen containing and the hyperbranched poly phosphamide carbon forming agent of benzene ring structure and preparation method thereof | |
| CN103113409A (en) | Triazine ring structure containing caged organic phosphate and preparation method thereof | |
| CN105295093A (en) | Ring phosphonitrile type additive flame retardant and preparation method thereof | |
| CN102924749B (en) | Ionic liquid-type phosphate fire retardant and preparation method thereof | |
| CN102627772B (en) | Method for synthesizing polymerized phenyl phosphonate by performing solid-liquid two-phase reaction | |
| CN109206665A (en) | A kind of hybrid modification hypo-aluminum orthophosphate and preparation method thereof | |
| CN105968410B (en) | One kind containing polyhydroxy, phosphorus system triazine ring expansion type flame retardant and preparation method | |
| CN102225998A (en) | Preparation method for pentaerythritol phosphoryl triethanolamide | |
| CN103254235B (en) | Butyl triazinyl triphenyl hypophosphite compound and preparation method thereof | |
| CN104693770A (en) | Halogen-free expansion type flame-retardant polycarbonate composite material and preparation method thereof | |
| CN102952290A (en) | Preparation method of novel synergistic intumescent flame retardant | |
| CN102796283A (en) | Compound intumescent flame retardant and preparation method thereof | |
| CN105646581B (en) | A kind of expansion type flame retardant and synthetic method of the halogen-free structure of cyanuric acid containing keto-acid | |
| CN103992512A (en) | Microencapsulated inorganic hypophosphite flame retardant and preparation method thereof | |
| CN106045928A (en) | Method for preparing triazine ring carbon-forming agent containing polyhydroxyl | |
| CN103254234B (en) | Methyl triazinyl triphenyl hypophosphite compound and preparation method thereof | |
| CN102942586B (en) | The preparation method of ethyl 2-methacrylate base phenmethyl phosphoric acid ester | |
| CN109796496A (en) | Three phosphazene derivative of ring containing alkoxy and its preparation method and application | |
| CN102532601A (en) | Novel halogen-free fire retardant ethanediamine diphenyl diphosphate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |