CN102952290B - The preparation method of synergistic intumescent flame retardant - Google Patents
The preparation method of synergistic intumescent flame retardant Download PDFInfo
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- CN102952290B CN102952290B CN201210374495.5A CN201210374495A CN102952290B CN 102952290 B CN102952290 B CN 102952290B CN 201210374495 A CN201210374495 A CN 201210374495A CN 102952290 B CN102952290 B CN 102952290B
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Abstract
The present invention provides a kind of preparation method of synergistic intumescent flame retardant, with 2,4,6 three (2,4 dihydroxy phenyls）1,3,5 triazine and annular phosphate are used as raw material.Present invention process is simple, and course of reaction is easy to control, and the fire retardant good thermal stability of synthesis, charring rate is high, and flame retarding efficiency is high.
Description
The invention belongs to flame retardant area, and in particular to the preparation method of synergistic intumescent flame retardant.
Current typical inflation type flame-retardant system such as APP (APP)/pentaerythrite (PER)/melamine (MEL) is acid
Source, carbon source and source of the gas multicomponent mixture, because addition component is more, the compatibility between each component and between component and matrix is deposited
In certain drawback, and then influence Flame Retardancy energy and physical and mechanical properties.Scientific experiment proves research and development collection carbon source, acid
Source, source of the gas realize that " three sources " effect functional group plays in one pack system intramolecular in the unimolecule expansion type flame retardant (IFR) of one
Expandable flame retardant effect and effect, can effectively solve fire retardant and high polymer material consistency problem, it is to avoid compound IFR is poly-
Migrated in compound, reduce fire retardant addition, it is significant to improving flame-retardant polymer efficiency.And contain triazine structure list
The expanding fire retardant flame retardant effect of member significantly, can be assigned steady by the excellent electrical property of ignition resistant substrate, mechanical property, splendid heat
It is qualitative, and with low toxicity, the advantages of cheap.
There is problem in the present invention, in order to solve prior art using 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5- tri-
There is provided go out two kinds of unimolecule expansion type flame retardants i.e. fire retardant 2,4,6- as initiation material of the invention for piperazine and annular phosphate
Three (2,4- bis- (the miscellaneous phosphinylidyne epoxide in oneself of 5,5- dimethyl -1,3- dioxy rings) phenyl) -1,3,5-triazines (TDDMDOBT) and resistance
Fire agent 2,4,6- tri- (2,4- bis- (5,5- dibromo methyl isophthalic acids, the miscellaneous phosphinylidyne epoxide in oneself of 3- dioxy rings) phenyl) -1,3,5-triazines
(TDDBDOBT), it is adaptable to the inflammable high polymer material such as polypropylene, polyethylene, epoxy resin, polyurethane foam it is flame-retardant modified.
The present invention provide two kinds of dendroid unimolecule P-N and P-N-Br synergistic intumescent flame retardant TDDMDOBT with
TDDBDOBT (structural formula is as follows) preparation method, both fire retardants are with 2,4,6 three (2,4- dihydroxy phenyl) -1,3,5- tri-
Piperazine and annular phosphate are used as raw material.Present invention process is simple, and course of reaction is easy to control, and the fire retardant heat endurance of synthesis is good
Good, charring rate is high, and flame retarding efficiency is high.
Fire retardant TDDMDOBT fire retardants TDDBDOBT
The present invention proposes two kinds of unimolecules P-N and P-N-Br synergistic intumescent flame retardant TDDMDOBT and TDDBDOBT, can
Prepared according to following technologies：
The preferable synthetic methods of fire retardant TDDMDOBT are：Material and cyclic phosphate containing polyhydroxy triazine structural units
Nucleophilic addition substitution reaction occurs in polar solvent for ester, and the fire retardant TDDMDOBT that the present invention is made is 2,4,6- tri- (2,4-
Two (the miscellaneous phosphinylidyne epoxide in oneself of 5,5- dimethyl -1,3- dioxy rings) phenyl) -1,3,5-triazines.
Final reacting product can be separated with classical method.Preferable method is that solvent is evaporated off, and obtains light yellow solid, to
Ethanol is added in reaction bulb, after solid dissolving, solvent is evaporated off again, the faint yellow solid slightly turned white, into reaction bulb
Distillation water cure is added, filtering obtains white product, product is made with ethyl alcohol recrystallization twice.
Unimolecule P-N synergistic intumescent flame retardants TDDMDOBT technology of preparing, obtained product are provided according to the present invention
With good heat endurance and into charcoal, molecular weight is 1293.7, and heat decomposition temperature is 257 DEG C, neat coal amout under nitrogen atmosphere
For 55.64%, phosphorus content is 14.38%.
The preferable synthetic methods of fire retardant TDDBDOBT are：Material containing polyhydroxy triazine structural units and bromination ring-type
Phosphate, occurs nucleophilic addition substitution reaction in polar solvent, and the fire retardant TDDBDOBT that the present invention is made is 2,4,6- tri-
(2,4- bis- (5,5- dibromo methyl isophthalic acids, the miscellaneous phosphinylidyne epoxide in oneself of 3- dioxy rings) phenyl) -1,3,5 triazines.
Final reacting product can be separated with classical method.Preferable method is that solvent is evaporated off, and obtains light yellow solid, to
Ethyl acetate is added in reaction bulb, after solid dissolving, solvent is evaporated off again, the faint yellow solid slightly turned white, to reaction
Distillation water cure is added in bottle, filtering obtains white product, product is made with ethyl alcohol recrystallization twice.
Unimolecule P-N-Br synergistic intumescent flame retardants TDDBDOBT technology of preparing, obtained production are provided according to the present invention
Product have good heat endurance and into charcoal, and molecular weight is 2240.6, and heat decomposition temperature is 334.55 DEG C under nitrogen atmosphere, into
Charcoal amount is 47.94%, and phosphorus content is 8.30%, and bromine content is 42.31%.
Following instance further illustrates preparation unimolecule P-N and P-N-Br synergistic intumescent flame retardants TDDMDOBT of the present invention
With TDDBDOBT preparation process, but these examples are not construed to limitation of the present invention in any sense.
The preparation of embodiment 1, TDDMDOBT
In 500mL four round flask, 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines 19.0g, 5 are added,
5- dimethyl -1,3- dioxaphosphorinane phosphoryl chloride phosphorus oxychlorides 73.6g, acetonitrile 300mL, stirring make it well mixed and fully dissolved,
Solution colour is in light yellow.Solution colour is deepened when reaction starts, and occurs a large amount of white smokes, subsequent solution in reaction bulb
Color gradually tends to be light yellow, and heating continues to react 24h, and it is suspension that ivory buff, which is presented, in solution, stops reaction.Solvent is steamed
Remove, obtain light yellow solid, ethanol 300mL is added into reaction bulb, after solid dissolving, solvent is evaporated off again, is slightly turned white
Faint yellow solid, into reaction bulb add distillation water cure, filtering, obtain white product, obtain white solid powder shape compound
That is fire retardant TDDMDOBT sterlings 55.0g, yield 90.5%, m.p.143~145 DEG C.
The preparation of embodiment 2, TDDBDOBT
In 500mL four round flask, 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines 10.5g, 5 are added,
5- dibromo methyl isophthalic acids, 3- dioxaphosphorinane phosphoryl chloride phosphorus oxychlorides 65.8g, acetonitrile 500mL, stirring makes it well mixed and fully molten
Solution, solution colour is in light yellow.Heating continues to react after 6h, stops reaction.After solvent is evaporated off, acetic acid is added into reaction bulb
Ethyl ester 300mL, after solid dissolving, is evaporated off solvent again, obtains white solid, filtering, obtains white solid powder shape compound
That is fire retardant TDDBDOBT sterlings 53.7g, yield 92.3%, m.p.133~135 DEG C.
Claims (4)
1. a kind of preparation method of synergistic intumescent flame retardant, it is characterised in that：Material containing polyhydroxy triazine structural units
It is synthesis material with 5,5- dimethyl -1,3- dioxaphosphorinanes phosphoryl chloride phosphorus oxychloride, polyhydroxy triazine structural units are 2,4,6- tri-
Nucleophilic addition occurs for (2,4- dihydroxy phenyl) -1,3,5-triazines and 5,5- dimethyl -1,3- dioxaphosphorinane phosphoryl chloride phosphorus oxychloride
Substitution reaction, be made fire retardant 2,4,6- tri- (2,4- bis- (the miscellaneous phosphinylidyne epoxide in oneself of 5,5- dimethyl -1,3- dioxy rings) phenyl) -
1,3,5-triazines.
2. a kind of preparation method of synergistic intumescent flame retardant, it is characterised in that：Material containing polyhydroxy triazine structural units
With 5,5- dibromo methyl isophthalic acids, 3- dioxaphosphorinanes phosphoryl chloride phosphorus oxychloride is synthesis material, and polyhydroxy triazine structural units are 2,4,6-
Nucleophilic occurs for three (2,4- dihydroxy phenyl) -1,3,5-triazines and 5,5- dibromo methyl isophthalic acid, 3- dioxaphosphorinanes phosphoryl chloride phosphorus oxychloride
Addition substitution reaction, is made (2,4- bis- (5,5- dibromo methyl isophthalic acids, the miscellaneous phosphinylidyne epoxides in oneself of 3- dioxy rings) of fire retardant 2,4,6- tri-
Phenyl) -1,3,5-triazines.
3. a kind of preparation method of synergistic intumescent flame retardant according to claim 1, it is characterised in that：In reaction vessel
2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines 19.0g of middle addition and 5,5- dimethyl -1,3- dioxaphosphorinane
Phosphoryl chloride phosphorus oxychloride 73.6g, makes it be sufficiently stirred for dissolving, 20~24h of heating response in 300mL anhydrous acetonitriles, until solution is presented shallow
During yellow-white suspension, stop reaction；Solvent is evaporated off, light yellow solid is obtained, the anhydrous second of 300mL is added into reaction vessel
Alcohol, after solid dissolving, is evaporated off solvent again, the faint yellow solid slightly turned white, and distilled water is added into reaction vessel and is consolidated
Change, filtering obtains white product, as 2,4,6- tri- (2,4- bis- (5,5- dimethyl -1,3- dioxy rings miscellaneous oneself in phosphinylidyne epoxide) benzene
Base) -1,3,5-triazines.
4. a kind of preparation method of synergistic intumescent flame retardant according to claim 2, it is characterised in that：In reaction vessel
2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines 10.5g of middle addition and 5,5- dibromo methyl isophthalic acid, 3- dioxy phospha hexamethylenes
Alkane phosphoryl chloride phosphorus oxychloride 65.8g, makes it be sufficiently stirred for dissolving in 500mL anhydrous acetonitriles, and 5~6h of heating response stops reaction；By solvent
It is evaporated off, 300ml ethyl acetate is added into reaction vessel by after solid dissolving, solvent is evaporated off again, white solid powder shape is obtained
Compound, i.e., 2,4,6- tri- (2,4- bis- (5,5- dibromo methyl isophthalic acids, the miscellaneous phosphinylidyne epoxide in oneself of 3- dioxy rings) phenyl) -1,3,5- tri-
Piperazine.
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| CN106854294A (en) * | 2017-01-05 | 2017-06-16 | 江南大学 | A kind of annular phosphate flame retardant and preparation method thereof |
| CN106892943B (en) * | 2017-03-07 | 2019-04-05 | 山东省化工研究院 | A kind of compound in triazine class, preparation method and applications |
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| 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;卢林刚等;《化学学报》;20120128;第70卷(第2期);第190-194页 * |
| 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;卢林刚等;《化学试剂》;20081015;第30卷(第10期);第721-724页 * |
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