CN106749415B - A kind of rhodamine B is modified three phosphonitrile of ring and its fire retardant and preparation method - Google Patents
A kind of rhodamine B is modified three phosphonitrile of ring and its fire retardant and preparation method Download PDFInfo
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- CN106749415B CN106749415B CN201611071761.1A CN201611071761A CN106749415B CN 106749415 B CN106749415 B CN 106749415B CN 201611071761 A CN201611071761 A CN 201611071761A CN 106749415 B CN106749415 B CN 106749415B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
Abstract
The invention discloses a kind of rhodamine Bs to be modified three phosphonitrile of ring and its fire retardant and preparation method, includes the following steps：A, in terms of mass parts, 1 part of hexachlorocyclotriph,sphazene is placed in the first container, adds 20~25 parts of toluene, is stirred continuously and fully dissolves, obtains solution A；B, 3.0~3.8 parts of rhodamine B amide is added in the solution A obtained into step a, is stirred continuously, obtains solution B；C, protective gas is passed through into the first container again, is to slowly warm up to 65~75 DEG C, then 13~16 parts of triethylamine is slowly added dropwise, is reacted 5.5~6.5 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, the solid of acquisition is modified three phosphonitrile fire retardant of ring for the rhodamine B.The beneficial effects of the invention are as follows：Heat resistance is good, and building-up process is simple, of low cost, has significant market competition advantage.
Description
Technical field
The present invention relates to a kind of fire retardant, especially a kind of rhodamine B is modified three phosphonitrile of ring and its fire retardant and preparation side
Method.
Background technology
Fire retardant, assigns the functional aid of combustible polymers flame retardancy, and fire-retardant primarily directed to high molecular material sets
Meter；There are many types for fire retardant, are divided into additive flame retardant and reactive flame retardant by application method.
Additive flame retardant is added in polymer by mechanical mix techniques, and polymer is made to have anti-flammability, mesh
Preceding additive flame retardant mainly has organic fire-retardant and inorganic combustion inhibitor, halogenated flame retardant (organic chloride and organic bromide)
With non-halogen.Organic is using bromine system, phosphorus nitrogen system, nitrogen system and red phosphorus and compound as some fire retardants of representative, and inorganic is mainly three
Aoxidize the flame-retardant systems such as two antimony, magnesium hydroxide, aluminium hydroxide, silicon systems.
Three phosphonitrile reagent of ring is the most representative compound of phosphonitrile, is established diplomatic relations by N, P atom by Dan Shuan for connection
Polymer, molecular formula Cl6N3P3Or (NPCl2)3.Three phosphonitrile of ring has the nitrogen and phosphorus of high-content, and the collaboration system formed has
Good flame retardant property, shows excellent noninflammability and flame retardant property, and oxygen index (OI) 25-65 is widely used in fire protection flame retarding material
Material and self-extinguishing.Therefore, such reagent is commonly used in heat-insulating material or fire proofing material (Hu Yuan Hu Jinliang, the clear fire of model dimension
Calamity science, 1996,5 (2), 12-16.).Such reagent is with flame retardant property is good, synthesis is simple, is easy to purification, of low cost etc.
Advantage, therefore the flame retardant property of many high molecular materials can be improved with three phosphazene derivative of ring.Phosphonitrile fire retardant due to phosphorus-
Nitrogen acts synergistically, and good flame retardation effect, smoke and toxic gas are few, therefore develops very fast.Phosphonitrile is as a kind of novel phosphorus nitrogen system
Fire retardant framework material, in molecular structure containing it is multiple can substituted Cl atoms, therefore can be prepared by MOLECULE DESIGN
Various functions sex flame retardant.(Hu Yuan, Shao's ancestor's dragon applied chemistries, 1998,15 (3):22-14.；Liu Yaqing, Wang Zhijun North China work
Institute's journal, 2003,24 (3):162-165).
Invention content
As it is various extensive and careful research and experiment as a result, present inventors have found that：Pass through Luo Dan
Bright B- amides have synthesized a kind of three phosphonitrile reagent of ring containing rhodamine B functional group with hexachlorocyclotriph,sphazene, and experiment shows this
Flame retardant property has been more than current commercial fire retardant, and the fire retardant heat resistance is good, and building-up process is simple, of low cost, tool
There is significant market competition advantage.
One object of the present invention provides a kind of rhodamine B and is modified three phosphonitrile of ring.
One object of the present invention provides a kind of fire retardant that three phosphonitrile of ring is modified comprising rhodamine B, has preferable resistance
Fuel efficiency fruit.
A further object of the invention provides a kind of preparation method that three phosphonitrile fire retardant of ring is modified comprising rhodamine B,
Building-up process is simple, of low cost, and the fire retardant performance of preparation is good.
To achieve the above object, a kind of rhodamine B of the present invention is modified three phosphonitrile of ring, and chemical structural formula is：
A kind of fire retardant is modified three phosphonitrile of ring comprising above-mentioned rhodamine B.
A kind of preparation method for the fire retardant that three phosphonitrile of ring is modified including rhodamine B, includes the following steps：
A, in terms of mass parts, 1 part of hexachlorocyclotriph,sphazene is placed in the first container, adds 20~25 parts of toluene,
It is stirred continuously and fully dissolves, obtain solution A；
B, 3.0~3.8 parts of rhodamine B-amide is added in the solution A obtained into step a, is stirred continuously, is obtained molten
Liquid B；
C, protective gas is passed through into the first container again, is to slowly warm up to 65~75 DEG C, then is slowly added dropwise 13~16 parts
Triethylamine reacts 5.5~6.5 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, obtain
The solid obtained is modified the fire retardant of three phosphonitrile of ring for the rhodamine B；
Wherein, the structural formula of the rhodamine B-amide is
Preferably, the preparation method of the hexachlorocyclotriph,sphazene includes：In terms of mass parts, 40 are added in into second container
The phosphorus pentachloride of part adds 50~60 parts of solvent, mixes and be stirred continuously, then 17~23 parts are added dropwise into second container
Pyridine obtains yellow liquid C；9~13 parts of ammonium chloride is added in into third container, 105~116 parts of solvent is added, mixes
Merge strong stirring, be heated to reflux condensing, obtain substance D；The yellow liquid C of acquisition is slowly added dropwise in the substance D,
It again after 40~80min of back flow reaction, is cooled to room temperature, adds 145~155 parts of water, extracted with low molecule alcohol, obtaining lower floor has
Machine phase, then be dried over anhydrous sodium sulfate；It at 50~60 DEG C, is evaporated under reduced pressure under -0.07~-0.09Mpa, is obtained after dry
Organic phase, then extracted with petroleum ether, 1.8~2.2h is heated to reflux at 75~85 DEG C of temperature, then at -20~0 DEG C, with just
After heptane recrystallizes three~five times, the hexachlorocyclotriph,sphazene is obtained；
Wherein, the solvent is any one in chlorine benzene,toluene,xylene；The low molecule alcohol is methanol, ethyl alcohol
In any one.
Preferably, the preparation method of the rhodamine B-amide：In terms of mass parts, described 3.6 parts of rhodamine B is added
Enter in the 4th container, add 28~36 parts of ethyl alcohol, then 8.1~9.2 parts of ethylenediamine is added dropwise, and be stirred continuously until being added dropwise
Terminate；At 75~85 DEG C, flow back 18~30h, and after reaction, reaction solution is cooled down, and removes solvent and obtains thick liquid；It will
The HCl solution of 0.5~1.5mol/L is added drop-wise in thick liquid, until pH reaches 9-10；It filters, clean, dry through decompression again
Afterwards, the rhodamine B-amide is obtained.
Preferably, it is characterised in that：Protective gas described in step C is nitrogen.
Preferably, it is characterised in that：The solvent is chlorobenzene.
Preferably, it is characterised in that：The low molecule alcohol is ethyl alcohol.
Preferably, it is characterised in that：The mass fraction ratio of the hexachlorocyclotriph,sphazene and rhodamine B-amide is 1：3.2
~3.6.
The beneficial effects of the invention are as follows：Heat resistance is good, and building-up process is simple, of low cost, competing with significant market
Strive advantage.
Description of the drawings
Rhodamine B prepared by Fig. 1 present invention is modified the infrared spectrum of three phosphonitrile of ring；
Rhodamine B prepared by Fig. 2 present invention is modified the DSC curve of three phosphonitrile of ring；
Rhodamine B prepared by Fig. 3 present invention is modified the hydrogen nuclear magnetic resonance spectrogram of three phosphonitrile of ring；
Rhodamine B prepared by Fig. 4 present invention is modified the carbon-13 nmr spectra figure of three phosphonitrile of ring.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, those skilled in the art's reference to be enabled to say
Bright book word can be implemented according to this.
Embodiment 1
(1) preparation of hexachlorocyclotriph,sphazene
The phosphorus pentachloride of 40g is added in into the second flask, the chlorobenzene of 55g is added, mixes and be stirred continuously, then to second
19.6g pyridines are added dropwise in flask, obtain yellow liquid C；The ammonium chloride of the drying of 11g is added in into third flask, is added
The chlorobenzene of 110g mixes simultaneously strong stirring, is heated to reflux condensing, obtains substance D；By the yellow liquid C of acquisition be slowly added dropwise into
It in the substance D, then after back flow reaction 60min, is cooled to room temperature, adds 150 parts of water, extracted with ethyl alcohol, obtaining lower floor has
Machine phase, then be dried over anhydrous sodium sulfate；It at 55 DEG C, is evaporated under reduced pressure under -0.08Mpa, organic phase is obtained, then use after dry
Petroleum ether is extracted, and 2h is heated to reflux at 80 DEG C of temperature, then at -15 DEG C, after being recrystallized four times with normal heptane, described in acquisition
Hexachlorocyclotriph,sphazene.In the process, reaction equation is as follows：
(2) preparation of rhodamine B amide
The 3.6g rhodamine Bs are added in the 4th flask, add 32g ethyl alcohol, then the ethylenediamine of 8.6g is added dropwise, not
Disconnected stirring is until completion of dropwise addition；At 80 DEG C, for 24 hours, after reaction, reaction solution is cooled down for reflux, and vacuum distillation removes solvent
Obtain thick liquid；The HCl solution of 1.0mol/L is added drop-wise in thick liquid, until PH reaches 9.5；It filters, steam through decompression again
Distilled water clean 3 times, dry after, obtain the rhodamine B-amide.In the process, reaction equation is as follows：
(3) rhodamine B is modified the preparation of three phosphonitrile fire retardant of ring
A, the hexachlorocyclotriph,sphazene of 1g is placed in the first flask, adds the toluene of 22g, be stirred continuously and fully molten
Solution obtains solution A；B, rhodamine B-amide of 3.4g is added in the solution A obtained into step a, is stirred continuously, obtains solution
B；C, the air being passed through again into the first flask in nitrogen the first flask of discharge, is to slowly warm up to 70 DEG C, then 14.6g is slowly added dropwise
Triethylamine, react 6 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, acquisition
Solid is modified three phosphonitrile fire retardant of ring for the rhodamine B.Reaction equation is as follows：
Embodiment 2
(1) preparation of hexachlorocyclotriph,sphazene
The phosphorus pentachloride of 40g is added in into the second flask, the chlorobenzene of 60g is added, mixes and be stirred continuously, then to second
17g pyridines are added dropwise in flask, obtain yellow liquid C；The ammonium chloride of the drying of 13g is added in into third flask, adds 105g
Chlorobenzene, mix and strong stirring, be heated to reflux condensing, obtain substance D；The yellow liquid C of acquisition is slowly added dropwise into described
Substance D in, then after back flow reaction 80min, be cooled to room temperature, add 145 parts of water, with methanol extraction, obtain lower floor's organic phase,
It is dried over anhydrous sodium sulfate again；It at 60 DEG C, is evaporated under reduced pressure under -0.09Mpa, organic phase is obtained, then use oil after dry
Ether is extracted, and 2.2h is heated to reflux at 75 DEG C of temperature, then at -20 DEG C, after being recrystallized three times with normal heptane, obtains described six
Three phosphonitrile of chlorine ring.
(2) preparation of rhodamine B amide
The 3.6g rhodamine Bs are added in the 4th flask, add 28g ethyl alcohol, then the ethylenediamine of 9.2g is added dropwise, not
Disconnected stirring is until completion of dropwise addition；At 75 DEG C, flow back 30h, and after reaction, reaction solution is cooled down, and vacuum distillation removes solvent
Obtain thick liquid；The HCl solution of 1.5mol/L is added drop-wise in thick liquid, until PH reaches 10；It is filtered again through decompression, distillation
Water clean 3 times, dry after, obtain the rhodamine B-amide.
(3) rhodamine B is modified the preparation of three phosphonitrile fire retardant of ring
A, the hexachlorocyclotriph,sphazene of 1g is placed in the first flask, adds the toluene of 20g, be stirred continuously and fully molten
Solution obtains solution A；B, rhodamine B-amide of 3.8g is added in the solution A obtained into step a, is stirred continuously, obtains solution
B；C, the air being passed through again into the first flask in nitrogen the first flask of discharge, is to slowly warm up to 65 DEG C, then be slowly added dropwise 16g's
Triethylamine reacts 5.5 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, acquisition
Solid is modified three phosphonitrile fire retardant of ring for the rhodamine B.
Embodiment 3
(1) preparation of hexachlorocyclotriph,sphazene
The phosphorus pentachloride of 40g is added in into the second flask, the chlorobenzene of 50g is added, mixes and be stirred continuously, then to second
23g pyridines are added dropwise in flask, obtain yellow liquid C；The ammonium chloride of the drying of 9g is added in into third flask, adds 116g's
Chlorobenzene mixes simultaneously strong stirring, is heated to reflux condensing, obtains substance D；The yellow liquid C of acquisition is slowly added dropwise into described in
It in substance D, then after back flow reaction 40min, is cooled to room temperature, adds 155 parts of water, with methanol extraction, obtain lower floor's organic phase, then
It is dried over anhydrous sodium sulfate；It at 50 DEG C, is evaporated under reduced pressure under -0.07Mpa, organic phase is obtained, then use petroleum ether after dry
It is extracted, 1.8h is heated to reflux at 85 DEG C of temperature, then at 0 DEG C, after being recrystallized five times with normal heptane, obtain the chlordene ring
Three phosphonitriles.
(2) preparation of rhodamine B amide
The 3.6g rhodamine Bs are added in the 4th flask, add 36g ethyl alcohol, then the ethylenediamine of 8.1g is added dropwise, not
Disconnected stirring is until completion of dropwise addition；At 85 DEG C, flow back 18h, and after reaction, reaction solution is cooled down, and vacuum distillation removes solvent
Obtain thick liquid；The HCl solution of 0.5mol/L is added drop-wise in thick liquid, until PH reaches 9；It is filtered again through decompression, distillation
Water clean 5 times, dry after, obtain the rhodamine B-amide.
(3) rhodamine B is modified the preparation of three phosphonitrile fire retardant of ring
A, the hexachlorocyclotriph,sphazene of 1g is placed in the first flask, adds the toluene of 25g, be stirred continuously and fully molten
Solution obtains solution A；B, rhodamine B-amide of 3.0g is added in the solution A obtained into step a, is stirred continuously, obtains solution
B；C, the air being passed through again into the first flask in nitrogen the first flask of discharge, is to slowly warm up to 75 DEG C, then be slowly added dropwise 13g's
Triethylamine reacts 6.5 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, acquisition
Solid is modified three phosphonitrile fire retardant of ring for the rhodamine B.
Embodiment 4
(1) preparation of hexachlorocyclotriph,sphazene
The phosphorus pentachloride of 40g is added in into the second flask, the chlorobenzene of 52g is added, mixes and be stirred continuously, then to second
18g pyridines are added dropwise in flask, obtain yellow liquid C；The ammonium chloride of the drying of 10g is added in into third flask, adds 106g
Chlorobenzene, mix and strong stirring, be heated to reflux condensing, obtain substance D；The yellow liquid C of acquisition is slowly added dropwise into described
Substance D in, then after back flow reaction 45min, be cooled to room temperature, add 148 parts of water, with methanol extraction, obtain lower floor's organic phase,
It is dried over anhydrous sodium sulfate again；It at 52 DEG C, is evaporated under reduced pressure under -0.075Mpa, organic phase is obtained, then use oil after dry
Ether is extracted, and 1.9h is heated to reflux at 82 DEG C of temperature, then at -5 DEG C, after being recrystallized four times with normal heptane, obtains described six
Three phosphonitrile of chlorine ring.
(2) preparation of rhodamine B amide
The 3.6g rhodamine Bs are added in the 4th flask, add 33g ethyl alcohol, then the ethylenediamine of 8.5g is added dropwise, not
Disconnected stirring is until completion of dropwise addition；At 82 DEG C, flow back 22h, and after reaction, reaction solution is cooled down, and vacuum distillation removes solvent
Obtain thick liquid；The HCl solution of 0.8mol/L is added drop-wise in thick liquid, until PH reaches 9.2；It filters, steam through decompression again
Distilled water clean 4 times, dry after, obtain the rhodamine B-amide.
(3) rhodamine B is modified the preparation of three phosphonitrile fire retardant of ring
A, the hexachlorocyclotriph,sphazene of 1g is placed in the first flask, adds the toluene of 23g, be stirred continuously and fully molten
Solution obtains solution A；B, rhodamine B-amide of 3.2g is added in the solution A obtained into step a, is stirred continuously, obtains solution
B；C, the air being passed through again into the first flask in nitrogen the first flask of discharge, is to slowly warm up to 72 DEG C, then be slowly added dropwise 15g's
Triethylamine reacts 5.8 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, acquisition
Solid is modified three phosphonitrile fire retardant of ring for the rhodamine B.
Embodiment 5
(1) preparation of hexachlorocyclotriph,sphazene
The phosphorus pentachloride of 40g is added in into the second flask, the chlorobenzene of 58g is added, mixes and be stirred continuously, then to second
22g pyridines are added dropwise in flask, obtain yellow liquid C；The ammonium chloride of the drying of 12g is added in into third flask, adds 115g
Chlorobenzene, mix and strong stirring, be heated to reflux condensing, obtain substance D；The yellow liquid C of acquisition is slowly added dropwise into described
Substance D in, then after back flow reaction 75min, be cooled to room temperature, add 153 parts of water, extracted with ethyl alcohol, obtain lower floor's organic phase,
It is dried over anhydrous sodium sulfate again；It at 58 DEG C, is evaporated under reduced pressure under -0.085Mpa, organic phase is obtained, then use oil after dry
Ether is extracted, and 2.1h is heated to reflux at 78 DEG C of temperature, then at -18 DEG C, after being recrystallized three times with normal heptane, obtains described six
Three phosphonitrile of chlorine ring.
(2) preparation of rhodamine B amide
The 3.6g rhodamine Bs are added in the 4th flask, add 31g ethyl alcohol, then the ethylenediamine of 8.3g is added dropwise, not
Disconnected stirring is until completion of dropwise addition；At 76 DEG C, flow back 29h, and after reaction, reaction solution is cooled down, and vacuum distillation removes solvent
Obtain thick liquid；The HCl solution of 1.4mol/L is added drop-wise in thick liquid, until PH reaches 9.9；It filters, steam through decompression again
Distilled water clean 4 times, dry after, obtain the rhodamine B-amide.
(3) rhodamine B is modified the preparation of three phosphonitrile fire retardant of ring
A, the hexachlorocyclotriph,sphazene of 1g is placed in the first flask, adds the toluene of 21g, be stirred continuously and fully molten
Solution obtains solution A；B, rhodamine B-amide of 3.7g is added in the solution A obtained into step a, is stirred continuously, obtains solution
B；C, the air being passed through again into the first flask in nitrogen the first flask of discharge, is to slowly warm up to 66 DEG C, then 14.5g is slowly added dropwise
Triethylamine, react 5.9 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, obtain
Solid for the rhodamine B be modified three phosphonitrile fire retardant of ring.
Embodiment 6
(1) preparation of hexachlorocyclotriph,sphazene
The phosphorus pentachloride of 40g is added in into the second flask, the chlorobenzene of 53.5g is added, mixes and be stirred continuously, then to the
22g pyridines are added dropwise in two flasks, obtain yellow liquid C；The ammonium chloride of the drying of 12g is added in into third flask, is added
The chlorobenzene of 113g mixes simultaneously strong stirring, is heated to reflux condensing, obtains substance D；By the yellow liquid C of acquisition be slowly added dropwise into
It in the substance D, then after back flow reaction 52min, is cooled to room temperature, adds 147 parts of water, extracted with ethyl alcohol, obtaining lower floor has
Machine phase, then be dried over anhydrous sodium sulfate；It at 51 DEG C, is evaporated under reduced pressure under -0.088Mpa, organic phase is obtained after dry, then
It is extracted with petroleum ether, 1.9h is heated to reflux at 83 DEG C of temperature, then at -6 DEG C, after being recrystallized three times with normal heptane, obtained
The hexachlorocyclotriph,sphazene.
(2) preparation of rhodamine B amide
The 3.6g rhodamine Bs are added in the 4th flask, add 32g ethyl alcohol, then the ethylenediamine of 8.7g is added dropwise, not
Disconnected stirring is until completion of dropwise addition；At 79 DEG C, flow back 23h, and after reaction, reaction solution is cooled down, and vacuum distillation removes solvent
Obtain thick liquid；The HCl solution of 1.2mol/L is added drop-wise in thick liquid, until PH reaches 9.2；It filters, steam through decompression again
Distilled water clean 4 times, dry after, obtain the rhodamine B-amide.
(3) rhodamine B is modified the preparation of three phosphonitrile fire retardant of ring
A, the hexachlorocyclotriph,sphazene of 1g is placed in the first flask, adds the toluene of 21g, be stirred continuously and fully molten
Solution obtains solution A；B, rhodamine B-amide of 3.6g is added in the solution A obtained into step a, is stirred continuously, obtains solution
B；C, the air being passed through again into the first flask in nitrogen the first flask of discharge, is to slowly warm up to 72 DEG C, then 13.5g is slowly added dropwise
Triethylamine, react 6.1 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, obtain
Solid for the rhodamine B be modified three phosphonitrile fire retardant of ring.
Embodiment 7
(1) preparation of hexachlorocyclotriph,sphazene
The phosphorus pentachloride of 40g is added in into the second flask, the chlorobenzene of 58.5g is added, mixes and be stirred continuously, then to the
19.5g pyridines are added dropwise in two flasks, obtain yellow liquid C；The ammonium chloride of the drying of 9.5g is added in into third flask, is added
The chlorobenzene of 107g mixes simultaneously strong stirring, is heated to reflux condensing, obtains substance D；By the yellow liquid C of acquisition be slowly added dropwise into
It in the substance D, then after back flow reaction 42min, is cooled to room temperature, adds 146 parts of water, extracted with ethyl alcohol, obtaining lower floor has
Machine phase, then be dried over anhydrous sodium sulfate；It at 51 DEG C, is evaporated under reduced pressure under -0.086Mpa, organic phase is obtained after dry, then
It is extracted with petroleum ether, 2.05h is heated to reflux at 76 DEG C of temperature, then at -18 DEG C, after being recrystallized four times with normal heptane, obtained
Obtain the hexachlorocyclotriph,sphazene.
(2) preparation of rhodamine B amide
The 3.6g rhodamine Bs are added in the 4th flask, add 33g ethyl alcohol, then the ethylenediamine of 8.8g is added dropwise, not
Disconnected stirring is until completion of dropwise addition；At 81 DEG C, flow back 26h, and after reaction, reaction solution is cooled down, and vacuum distillation removes solvent
Obtain thick liquid；The HCl solution of 0.7mol/L is added drop-wise in thick liquid, until PH reaches 9.5；It filters, steam through decompression again
Distilled water clean 3 times, dry after, obtain the rhodamine B-amide.
(3) rhodamine B is modified the preparation of three phosphonitrile fire retardant of ring
A, the hexachlorocyclotriph,sphazene of 1g is placed in the first flask, adds the toluene of 21.5g, be stirred continuously and fully molten
Solution obtains solution A；B, rhodamine B-amide of 3.1g is added in the solution A obtained into step a, is stirred continuously, obtains solution
B；C, the air being passed through again into the first flask in nitrogen the first flask of discharge, is to slowly warm up to 66 DEG C, then 14.5g is slowly added dropwise
Triethylamine, react 6.2 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, obtain
Solid for the rhodamine B be modified three phosphonitrile fire retardant of ring.
Data analysis
Respectively to as the rhodamine B obtained by embodiment 1-7 be modified ring three phosphonitrile fire retardant carry out infrared spectrum, DSC tests,
Nuclear magnetic resonance spectroscopy is tested and carbon-13 nmr spectra test, obtains Fig. 1-4.
As shown in Figure 1, in 3396cm-1、2931cm-1、2969cm-1For N-H absorption peaks, 949cm-1For phenyl ring absorption peak,
1118cm-1For C-O-C absorption peaks, 1681cm-1For carbonyl absorption peak, 1219cm-1For P=N absorption peaks, 820cm-1 is inhaled for P-N
Peak is received, 513cm-1,578cm-1 are P-Cl absorption peaks.
As shown in Figure 2, the temperature of thermal decomposition is 286.5 DEG C.
From the figure 3, it may be seen that 1H NMR (CDCl3-d3,ppm):Chemical shift δ=7.5~7.0ppm is above independent phenyl ring
Hydrogen environment；Chemical shift δ=6.5~6.2ppm characterizations are the hydrogen environment of phenyl ring (being connected with epoxy alicyclic) above；Chemical potential
It is the hydrogen environment above epoxy alicyclic to move δ=3.5~3.2ppm；Chemical shift δ=2.3ppm is solvent peak；Chemical shift δ=
1.4~1.1ppm is methyl and the hydrogen environment above methylene.Chemical shift δ=0.02ppm is standard specimen peak.
As shown in Figure 4,13C NMR (CDCl3-d3,ppm):Chemical shift δ=154.0~148.8ppm is on epoxy alicyclic
The C environment in face；；What chemical shift δ=135.0~122.0ppm was characterized is the C environment above independent phenyl ring；Chemical shift δ=
110.0~105.0ppm is the C environment for being connected nearer with substituent group above phenyl ring；Chemical shift δ=77.0ppm is molten on nearby
Agent peak；Chemical shift δ=45.8~39.1ppm is methyl and the C environment above methylene.Chemical shift δ=12.6ppm is end
C peaks above terminal methyl.
It is applied in epoxy resin to being modified three phosphonitrile fire retardant of ring as the rhodamine B obtained by embodiment 1-7 respectively, carries out
Oxygen index (OI) is tested, and the results are shown in Table one.
| Project | Oxygen index (OI) |
| Pure epoxy resin | 20.7±0.1 |
| Embodiment 1 | 24.10 |
| Embodiment 2 | 24.06 |
| Embodiment 3 | 23.98 |
| Embodiment 4 | 24.05 |
| Embodiment 5 | 24.09 |
| Embodiment 6 | 24.08 |
| Embodiment 7 | 23.98 |
As shown in Table 1, the oxygen index (OI) that the rhodamine B prepared according to the present invention is modified three phosphonitrile fire retardant of ring can reach 24
±0.1.And the oxygen index (OI) of the fire retardant of pure epoxy resin class is 20.7 ± 0.1, existing commercialization fire retardant oxygen index (OI) can reach
To 23.7 ± 0.1, it can be seen that, the oxygen index (OI) performance of fire retardant prepared by the present invention is substantially better than existing fire retardant.
As described above, a kind of rhodamine B of the present invention is modified three phosphonitrile fire retardant of ring, building-up process good with heat resistance
Simply, it is of low cost, there is significant market competition advantage.
Although the embodiments of the present invention have been disclosed as above, but it is not restricted to listed fortune in bright book and embodiment
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily real
Now other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is not limited to
Specific details.
Claims (9)
1. a kind of rhodamine B is modified three phosphonitrile of ring, which is characterized in that its chemical structural formula：
。
2. a kind of fire retardant, it is characterised in that：Three phosphonitrile of ring is modified including the rhodamine B described in claim 1.
3. a kind of rhodamine B as described in claim 1 is modified the preparation method of three phosphonitrile of ring, which is characterized in that it includes
Following steps：
A, in terms of mass parts, 1 part of hexachlorocyclotriph,sphazene is placed in the first container, adds 20~25 parts of toluene, no
It is disconnected to stir and fully dissolve, obtain solution A；
B, 3.0~3.8 parts of rhodamine B-amide is added in the solution A obtained into step a, is stirred continuously, obtains solution
B；
C, protective gas is passed through into the first container again, is to slowly warm up to 65~75 DEG C, then 13~16 parts of three second are slowly added dropwise
Amine reacts 5.5~6.5 hours；After reaction, it treats that reaction solution cooling is poured into water, there are a large amount of solids to be precipitated, obtain
Solid for rhodamine B be modified three phosphonitrile of ring；
Wherein, the structural formula of the rhodamine B-amide is。
A kind of 4. preparation method as claimed in claim 3, which is characterized in that the preparation method packet of the hexachlorocyclotriph,sphazene
It includes：In terms of mass parts, 40 parts of phosphorus pentachloride is added in into second container, 50~60 parts of solvent is added, mixes and continuous
It stirs, then 17~23 parts of pyridine is added dropwise into second container, obtain yellow liquid C；9~13 parts are added in into third container
Ammonium chloride adds 105~116 parts of solvent, mixes simultaneously strong stirring, is heated to reflux condensing, obtains substance D；By acquisition
Yellow liquid C is slowly added dropwise in the substance D, then after 40~80min of back flow reaction, is cooled to room temperature, and adds 145~155
The water of part, is extracted with low molecule alcohol, obtains lower floor's organic phase, then be dried over anhydrous sodium sulfate；At 50~60 DEG C, -0.07
It is evaporated under reduced pressure under~-0.09Mpa, organic phase is obtained, then extracted with petroleum ether after dry, at 75~85 DEG C of temperature
1.8~2.2h is heated to reflux, then at -20~0 DEG C, after being recrystallized three~five times with normal heptane, obtains three phosphorus of chlordene ring
Nitrile；
Wherein, the solvent is any one in chlorine benzene,toluene,xylene；The low molecule alcohol is methanol, in ethyl alcohol
Any one.
5. preparation method as claimed in claim 3, which is characterized in that the preparation method of the rhodamine B-amide：With quality
Part meter, described 3.6 parts of rhodamine B is added in the 4th container, adds 28~36 parts of ethyl alcohol, then be added dropwise 8.1~9.2 parts
Ethylenediamine, and be stirred continuously until completion of dropwise addition；At 75~85 DEG C, flow back 18~30h, after reaction, by reaction solution
Cooling removes solvent and obtains thick liquid；The HCl solution of 0.5~1.5mol/L is added drop-wise in thick liquid, until pH reaches 9-
10；Again after decompression filters, cleans, dries, the rhodamine B-amide is obtained.
6. preparation method as claimed in claim 3, it is characterised in that：Protective gas described in step C is nitrogen.
7. preparation method as claimed in claim 4, it is characterised in that：The solvent is chlorobenzene.
8. preparation method as claimed in claim 4, it is characterised in that：The low molecule alcohol is ethyl alcohol.
9. preparation method as claimed in claim 3, it is characterised in that：The matter of the hexachlorocyclotriph,sphazene and rhodamine B-amide
It is 1 to measure score ratio：3.2~3.6.
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| CN102503982A (en) * | 2011-10-31 | 2012-06-20 | 华中师范大学 | Phosphonitrilic chloride trimer epoxy compound with flame-retardant property and preparation and application thereof |
| CN104403128A (en) * | 2014-10-30 | 2015-03-11 | 东北林业大学 | Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant |
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| CN102503982A (en) * | 2011-10-31 | 2012-06-20 | 华中师范大学 | Phosphonitrilic chloride trimer epoxy compound with flame-retardant property and preparation and application thereof |
| CN104403128A (en) * | 2014-10-30 | 2015-03-11 | 东北林业大学 | Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant |
Non-Patent Citations (2)
| Title |
|---|
| "基于环三磷腈/磷酸酯反应型磷-氮阻燃剂的合成、热降解及应用";胡文田等;《化工学报》;20150531;第66卷(第5期);第1976-1981页 * |
| "环三磷腈类阻燃剂的合成及应用研究进展";游歌云等;《应用化学》;20140930;第31卷(第9期);第993-1006页 * |
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