CN106832404B - Surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof - Google Patents
Surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof Download PDFInfo
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- CN106832404B CN106832404B CN201710066383.6A CN201710066383A CN106832404B CN 106832404 B CN106832404 B CN 106832404B CN 201710066383 A CN201710066383 A CN 201710066383A CN 106832404 B CN106832404 B CN 106832404B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 67
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000005012 migration Effects 0.000 title claims abstract description 38
- 238000013508 migration Methods 0.000 title claims abstract description 38
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000013067 intermediate product Substances 0.000 claims abstract description 12
- QJXCFMJTJYCLFG-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzaldehyde Chemical compound FC1=C(F)C(F)=C(C=O)C(F)=C1F QJXCFMJTJYCLFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 239000012757 flame retardant agent Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- UVUCUHVQYAPMEU-UHFFFAOYSA-N 3-[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound NC1=CC=CC(C(C=2C=C(N)C=CC=2)(C(F)(F)F)C(F)(F)F)=C1 UVUCUHVQYAPMEU-UHFFFAOYSA-N 0.000 abstract 1
- 230000006872 improvement Effects 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 1
- JRHNUZCXXOTJCA-UHFFFAOYSA-N 1-fluoropropane Chemical compound CCCF JRHNUZCXXOTJCA-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- -1 alkene Hydrocarbon Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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 Table
- 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
- C07F9/6571—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 oxygen atoms as the only ring hetero atoms
- C07F9/657163—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses surface migration sex flame retardants of a kind of Nitrogen-and Phosphorus-containing and preparation method thereof, preparation method includes the following steps: (1) by 2, bis- (3- aminophenyl) hexafluoropropane of 2- and pentafluorobenzaldehyde heat in a solvent, after reaction, the reaction system containing intermediate product I is obtained;(2) DOPO is added in the reaction system containing intermediate product I that step (1) obtains and is heated, after reaction, washing, drying obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing.A kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof, with the increase of phosphorus content in solidfied material, the anti-flammability of solidfied material increases;When flame retardant agent content reaches 5-10%, solidfied material can achieve UL-94, and V-0 grades, good flame retardation effect.The preparation method can quickly produce the surface migration sex flame retardant product of Nitrogen-and Phosphorus-containing, and processing step is succinct, it is easy to accomplish, productivity is high.
Description
Technical field
The present invention relates to technical field of flame retardant, and in particular to a kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and its preparation
Method.
Background technique
Halogenated flame retardant is containing halogens and with a based flame retardant of halogens fire retardation.Four kinds of halogen system
Halogen system element fluorine (F), chlorine (Cl), bromine (Br), iodine (I) all have anti-flammability, and flame retardant effect is successively increased by the sequence of F, Cl, Br, I
By force.It is most strong with iodine flame retardant.In production, only chlorine class and brominated flame retardant are widely used and fluorine class and iodine based flame retardant
Rare application, this is because C-F key is too strong and cannot effectively capture the C-I key of free radical and the fire retardant containing I in fluorine-containing fire retardant
Too weak easily being destroyed affects polymer performance (such as photostability), has lost flame retardant property just below degradation temperature.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviation DOPO contain P-H key in structure, to alkene
Hydrocarbon, epoxide and the great activity of carbonyls can react and generate many derivatives.DOPO and its derivative are due to molecule
Contain cyclohexyl biphenyl, phenanthrene ring, O=P-O key in structure, so there is stronger flame retardant property than common organophosphorus ester.By
Saito reported its synthetic route in 1972 for the first time.DOPO and its derivative can be used as response type and additive flame retardant, close
At fire retardant Halogen, smokeless, nontoxic, do not migrate, flame retardant property is lasting.While improving the flame retardant property of material, not shadow
Ring the mechanical performances such as the mechanical strength of material.It can be used for the multiple materials such as polyamide, linear polyester, polyurethane, epoxy resin
Flame retardant treatment, foreign countries are widely used in the fire-retardant of materials such as pressurized layer, circuit board in plastics for electronics, brass.Although having
Good flame retardant property, but with the increase of additional amount, some detrimental effects can be brought to the performance of material itself.
Summary of the invention
In view of the above deficiencies, it is an object of the present invention to provide a kind of formula is reasonable, it is easy to accomplish, flame retardant effect
The surface migration sex flame retardant of good Nitrogen-and Phosphorus-containing.
The second object of the present invention is, provide it is a kind of can quick Fabrication go out the surface migration sex flame retardant of above-mentioned Nitrogen-and Phosphorus-containing
Preparation method, with the increase of phosphorus content in solidfied material, the anti-flammability of solidfied material increases;When flame retardant agent content reaches 5~
When 10%, solidfied material can achieve UL94, and V-0 grades.
To achieve the above object, the technical solution provided by the present invention is: a kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing,
Its structural formula is as follows:
A kind of preparation method of the surface migration sex flame retardant of above-mentioned Nitrogen-and Phosphorus-containing comprising following steps:
(1) bis- (4- aminophenyl) hexafluoropropane of 2,2- and pentafluorobenzaldehyde are heated in a solvent, after reaction, is obtained
Reaction system containing intermediate product I;
(2) DOPO is added in the reaction system containing intermediate product I that step (1) obtains and is heated, after reaction,
Washing, drying, obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing.
Its reaction process are as follows:
As an improvement of the present invention, bis- (4- aminophenyl) hexafluoropropane of 2,2- and phenyl-pentafluoride in the step (1)
The molar ratio of formaldehyde is 1:2.
As an improvement of the present invention, the reaction time is 8~10h in the step (1).
As an improvement of the present invention, heating temperature is 62~68 DEG C in the step (1), preferably, heating temperature
Preferably 65 DEG C.
As an improvement of the present invention, solvent is ethyl alcohol, DMF or DMSO in the step (1).
As an improvement of the present invention, the additional amount of solvent is bis- (the 4- aminophenyls) six of 2,2- in the step (1)
6~12 times of fluoro-propane and pentafluorobenzaldehyde quality sum.
As an improvement of the present invention, mole of the DOPO in the step (2) and the pentafluorobenzaldehyde in step (1)
Than for 1:1.
As an improvement of the present invention, the reaction temperature in the step (2) is 62~68 DEG C, preferably, heating temperature
Preferably 65 DEG C of degree.
As an improvement of the present invention, the reaction time in the step (2) is 4~6h.
The invention has the benefit that the formula of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing provided by the invention is reasonable, draw
A large amount of fluorine element is entered, can make fire retardant that there is certain surface migration in solidfied material, make fire retardant in solidfied material
Content gradually increase from inside to outside, make solidfied material surface highest containing flame retardant amount, keep its additive amount low, flame retardant effect is excellent;
Although introducing fluorine element on fire retardant simultaneously, free radical cannot be effectively captured since C-F key is too strong, makes fire retardant
With excellent thermal stability;With the increase of phosphorus content in solidfied material, the anti-flammability of solidfied material increases;When flame retardant agent content reaches
To 5~10% when (phosphorus content is 0.25wt%~0.5wt%), solidfied material can achieve UL-94, and V-0 grades, good flame retardation effect.
Preparation method provided by the invention can quickly produce the surface migration sex flame retardant product of Nitrogen-and Phosphorus-containing, and processing step is succinct, easily
In realization, productivity is high.
With reference to the accompanying drawings and examples, the present invention is further described.
Detailed description of the invention
Fig. 1 is nuclear magnetic spectrogram of the invention.
Specific embodiment
A kind of embodiment 1: synthesis step of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing are as follows:
(1) 145g by the pentafluorobenzaldehyde of bis- (4- aminophenyl) hexafluoropropane of the 2,2- of 11.1g and 13.1g at 65 DEG C
8h is heated in ethyl alcohol, after reaction, obtains the reaction system containing intermediate product I;
(2) DOPO of 14.4g is added in the reaction system containing intermediate product I that step (1) obtains in 65 DEG C of items
4h is heated under part, and after reaction, washing, drying obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, yield 83.4%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3410cm-1, C-N characteristic peak 1288cm-1, P-O-C characteristic peak 1032cm-1,
P-O-Ph characteristic peak 1231cm-1, P-Ph characteristic peak 1595cm-1, P=O characteristic peak 1212cm-1。
Nuclear magnetic spectrogram as shown in Figure 1, nuclear-magnetism test result is as follows:
1H-NMR (400MHz, DMSO-d6) δ 7.50 (k, 2H), 7.30-7.31 (j, 6H), 7.20 (i, 2H), 7.05 (g,
2H), 6.91 (f, 4H), 6.88 (e, 2H), 6.79 (d, 2H), 6.35 (c, 4H), 4.00 (b, 2H), 3.90 (a, 2H).
A kind of embodiment 2: synthesis step of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing are as follows:
(1) by the pentafluorobenzaldehyde of bis- (4- aminophenyl) hexafluoropropane of the 2,2- of 13.36g and 15.68g at 65 DEG C
10h is heated in 232gDMF, after reaction, obtains the reaction system containing intermediate product I;
(2) DOPO of 17.28g is added in the reaction system containing intermediate product I that step (1) obtains in 65 DEG C of items
6h is heated under part, and after reaction, washing, drying obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, yield 89.6%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3390cm-1, C-N characteristic peak 1268cm-1, P-O-C characteristic peak 1031cm-1,
P-O-Ph characteristic peak 1231cm-1, P-Ph characteristic peak 1595cm-1, P=O characteristic peak 1208cm-1。
A kind of embodiment 3: synthesis step of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing are as follows:
(1) by the pentafluorobenzaldehyde of bis- (4- aminophenyl) hexafluoropropane of the 2,2- of 8.35g and 9.8g at 65 DEG C
9h is heated in 217.8gDMSO, after reaction, obtains the reaction system containing intermediate product I;
(2) DOPO of 10.8g is added in the reaction system containing intermediate product I that step (1) obtains in 65 DEG C of items
5h is heated under part, and after reaction, washing, drying obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, yield 87.2%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3370cm-1, C-N characteristic peak 1292cm-1, P-O-C characteristic peak 1032cm-1,
P-O-Ph characteristic peak 1231cm-1, P-Ph characteristic peak 1595cm-1, P=O characteristic peak 1215cm-1。
Application Example:
Material is weighed according to table 1:
Table 1
The surface migration sex flame retardant and polystyrene of Nitrogen-and Phosphorus-containing are uniformly mixed;It adds twin-screw extrude, in machine
Under conditions of organizing 200-220 DEG C of temperature, 210 DEG C of die head temperature, screw speed 200rpm, extruding pelletization, then through drying, cool down,
Obtain fire retardant polystyrene sample.UL94 testing vertical flammability is carried out to the sample, as a result shown in table 2:
Table 2
Above-described embodiment is only the preferable embodiment of the present invention, and the present invention cannot enumerate out whole embodiment party
Formula, all technical solutions using one of above-described embodiment, or the equivalent variations done according to above-described embodiment are protected in the present invention
It protects in range.
Specifically, the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing provided by the invention has the advantage that
(1) the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing of the invention, with the increase of phosphorus content in solidfied material, solidification
The anti-flammability of object increases;When flame retardant agent content reaches 5~10% (phosphorus content 0.25wt%-0.5wt%), solidfied material can be with
Reach UL-94, V-0 grades.
(2) the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing of the invention, introduces a large amount of fluorine element, can make fire-retardant
Agent has certain surface migration in solidfied material, gradually increases the content of fire retardant in solidfied material from inside to outside, makes solid
Compound surface highest containing flame retardant amount, keeps its additive amount low, flame retardant effect is excellent.
(3) the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing of the invention, although introducing fluorine element on fire retardant,
It is that cannot effectively capture free radical since C-F key is too strong, makes fire retardant that there is excellent thermal stability.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification
Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.Such as the present invention
Described in above-described embodiment, existed using other fire retardants obtained from same or similar method and component and preparation method thereof
In the scope of the present invention.
Claims (10)
1. a kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, which is characterized in that its structural formula is as follows:
2. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing described in claim 1, it is characterised in that: it includes
Following steps:
(1) bis- (4- aminophenyl) hexafluoropropane of 2,2- and pentafluorobenzaldehyde are heated in a solvent, after reaction, must be contained
The reaction system of intermediate product I;
(2) DOPO is added in the reaction system containing intermediate product I that step (1) obtains and is heated, after reaction, washed
It washs, dry, obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing.
3. the preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing according to claim 2, it is characterised in that: the step
Suddenly bis- (4- aminophenyl) hexafluoropropane of 2,2- and the molar ratio of pentafluorobenzaldehyde are 1:2 in (1).
4. the preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing according to claim 2, it is characterised in that: the step
Suddenly the reaction time is 8~10h in (1).
5. the preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing according to claim 2, it is characterised in that: the step
Suddenly heating temperature is 62~68 DEG C in (1).
6. the preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing according to claim 2, it is characterised in that: the step
Suddenly solvent is ethyl alcohol, DMF or DMSO in (1).
7. the preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing according to claim 2, it is characterised in that: the step
Suddenly the additional amount of solvent is 6~12 times of bis- (4- aminophenyl) hexafluoropropane of 2,2- and pentafluorobenzaldehyde quality sum in (1).
8. the preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing according to claim 2 or 3, it is characterised in that: institute
The molar ratio for stating the DOPO in step (2) and the pentafluorobenzaldehyde in step (1) is 1:1.
9. the preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing according to claim 2, it is characterised in that: the step
Suddenly the reaction temperature in (2) is 62~68 DEG C.
10. the preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing according to claim 2, it is characterised in that: described
Reaction time in step (2) is 4~6h.
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