CN106905369A - A kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof - Google Patents
A kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof Download PDFInfo
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- CN106905369A CN106905369A CN201710119856.4A CN201710119856A CN106905369A CN 106905369 A CN106905369 A CN 106905369A CN 201710119856 A CN201710119856 A CN 201710119856A CN 106905369 A CN106905369 A CN 106905369A
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- flame retardant
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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
- C07F9/6571—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)
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- 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'
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
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, its structural formula is as follows：A kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, comprises the following steps：(1) by tricresyl phosphate (4 aminophenyl) ester and 3, the formaldehyde of 5 difluoro pyridine 4 is heated in a solvent, after reaction terminates, obtains the reaction system containing intermediate product I；(2) DOPO is added in the reaction system containing intermediate product I that step (1) is obtained and is heated, after reaction terminates, washed, dry, obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing.Surface migration sex flame retardant of a kind 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 reach UL 94,0 grade of V.
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 technology
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 increased successively by the order 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, because C-F keys are too strong and can not effectively catch free radical and contain the C-I keys of I fire retardants in fluorine-containing fire retardant
Too weak easily destroyed have impact on polymer performance (such as photostability), fire resistance has just been lost below degradation temperature.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviation DOPO contains P-H keys, to alkene in its structure
Hydrocarbon, epoxide and the great activity of carbonyls, can react many derivatives of generation.DOPO and its derivative are due to molecule
Contain cyclohexyl biphenyl, phenanthrene ring, O=P-O keys in structure, so there is stronger fire resistance than common organophosphorus ester.By
Saito reported its synthetic route first in 1972.DOPO and its derivative can be used as response type and additive flame retardants, its conjunction
Into fire retardant Halogen, smokeless, nontoxic, do not migrate, fire resistance is lasting.While the fire resistance of material is improved, 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 the material such as laminate layer, circuit board in plastics for electronics, brass.Although having
Good fire resistance, but with the increase of addition, some detrimental effects can be brought to material performance in itself.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided a kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and
Its preparation method, with the increase of phosphorus content in solidfied material, the anti-flammability of solidfied material increases；When flame retardant agent content reaches 5-10%
When, solidfied material can reach UL94, V-0 grades.
To realize the purpose of the present invention, the present invention is adopted the following technical scheme that：
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 Nitrogen-and Phosphorus-containing, comprises the following steps：
(1) tricresyl phosphate (4- aminophenyls) ester and 3,5- difluoro pyridine -4- formaldehyde are heated in a solvent, reaction terminates
Afterwards, the reaction system containing intermediate product I is obtained；
(2) DOPO is added in the reaction system containing intermediate product I that step (1) is obtained and is heated, after reaction terminates,
Wash, dry, obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing.
Its course of reaction is：
Specifically, in above-mentioned steps (1) tricresyl phosphate (4- aminophenyls) ester and 3,5- difluoro pyridine -4- formaldehyde mol ratio
It is 1:3.
Specifically, the reaction time is 7-12h in above-mentioned steps (1).
Specifically, heating-up temperature is 70 DEG C in above-mentioned steps (1).
Specifically, solvent is ethanol, DMF or DMSO in above-mentioned steps (1).
Specifically, in above-mentioned steps (1) solvent addition for tricresyl phosphate (4- aminophenyls) ester and 3,5- difluoro pyridine-
6-12 times of 4- formaldehyde quality sums.
Specifically, the mol ratio of 3, the 5- difluoro pyridine -4- formaldehyde in the DOPO and step (1) in above-mentioned steps (2) is
1:1。
Specifically, the reaction temperature in above-mentioned steps (2) is 70 DEG C.
Specifically, the reaction time in above-mentioned steps (2) is 4-8h.
The device have the advantages 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 increase of thing；When flame retardant agent content reaches 5-10% (phosphorus content is 0.44wt%-0.89wt%), 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, with high flame retardant, low cigarette, low toxicity evil, without corruption
Corrosion gas is produced.
(3) a kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing of the invention, contains fluorine atom in structure, due to C-F keys too
Free radical can not be effectively caught by force, makes fire retardant that there is preferable heat endurance, ultraviolet radiation resisting is acted on light stabilizer
Influence is small.
(4) raw material used in the present invention is easy to get, process is simple, low cost, is easy to industrialized production.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the surface migration sex flame retardant nuclear magnetic spectrogram of the Nitrogen-and Phosphorus-containing of the specific embodiment of the invention 1.
Specific embodiment
Presently in connection with embodiment, the present invention is further detailed explanation.
Embodiment 1
A kind of synthesis step of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing is：
(1) by the 3,5- difluoro pyridine -4- formaldehyde of tricresyl phosphate (4- aminophenyls) ester of 11.1g and 12.9g at 70 DEG C
7h is heated in 144g ethanol, after reaction terminates, the reaction system containing intermediate product I is obtained；
(2) DOPO of 19.5g is added in the reaction system containing intermediate product I that step (1) is obtained in 70 DEG C of bars
4h heating under part, after reaction terminates, washs, dries, and obtains the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, yield 84.9%.
Its infrared test result is as follows：
FTIR(KBr)：N-H stretching vibration peaks 3410cm-1, C-H stretching vibration peaks 3075cm-1, C-N characteristic peaks 1289cm-1, C-F characteristic peaks 1100cm-1, P-O-C characteristic peaks 1032cm-1, P-O-Ph characteristic peaks 1231cm-1, P-Ph characteristic peaks 1595cm-1, P=O characteristic peaks 1212cm-1, the out-of-plane bending vibration peak 900cm of fragrant hydrogen-1。
Nuclear magnetic spectrogram is as shown in figure 1, nuclear-magnetism test result is as follows：
1H-NMR (400MHz, DMSO-d6) δ 8.08 (6H), 7.5 (3H), 7.3-7.31 (3H), 7.20 (3H), 7.05
(3H), 6.88 (3H), 6.82 (6H), 6.79 (3H), 6.51 (4H), 6.26 (4H), 4.01 (3H), 3.91 (3H).
Embodiment 2
A kind of synthesis step of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing is：
(1) by the 3,5- difluoro pyridine -4- formaldehyde of tricresyl phosphate (4- aminophenyls) ester of 18.6g and 21.5g at 70 DEG C
10h is heated in 401g DMF, after reaction terminates, the reaction system containing intermediate product I is obtained；
(2) DOPO of 32.4g is added in the reaction system containing intermediate product I that step (1) is obtained in 70 DEG C of bars
6h heating under part, after reaction terminates, washs, dries, and obtains the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, yield 84.8%.
Its infrared test result is as follows：
FTIR(KBr)：N-H stretching vibration peaks 3415cm-1, C-H stretching vibration peaks 3075cm-1, C-N characteristic peaks 1289cm-1, C-F characteristic peaks 1100cm-1, P-O-C characteristic peaks 1033cm-1, P-O-Ph characteristic peaks 1231cm-1, P-Ph characteristic peaks 1590cm-1, P=O characteristic peaks 1212cm-1, the out-of-plane bending vibration peak 850cm of fragrant hydrogen-1。
Embodiment 3
A kind of synthesis step of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing is：
(1) by the 3,5- difluoro pyridine -4- formaldehyde of tricresyl phosphate (4- aminophenyls) ester of 37.1g and 42.9g at 70 DEG C
12h is heated in 960g DMSO, after reaction terminates, the reaction system containing intermediate product I is obtained；
(2) DOPO of 64.9g is added in the reaction system containing intermediate product I that step (1) is obtained in 70 DEG C of bars
8h heating under part, after reaction terminates, washs, dries, and obtains the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, yield 84.6%.
Its infrared test result is as follows：
FTIR(KBr)：N-H stretching vibration peaks 3420cm-1, C-H stretching vibration peaks 3080cm-1, C-N characteristic peaks 1288cm-1, C-F characteristic peaks 1100cm-1, P-O-C characteristic peaks 1033cm-1, P-O-Ph characteristic peaks 1231cm-1, P-Ph characteristic peaks 1590cm-1, P=O characteristic peaks 1212cm-1, the out-of-plane bending vibration peak 800cm of fragrant hydrogen-1。
Application Example：
Material is weighed according to table 1：
Table 1：
| Application Example | Surface migration sex flame retardant (g) of Nitrogen-and Phosphorus-containing | Polystyrene (g) | P content |
| Application Example 1 | 30 | 970 | 0.27wt% |
| Application Example 2 | 40 | 960 | 0.36wt% |
| Application Example 3 | 50 | 950 | 0.44wt% |
| Application Example 4 | 80 | 920 | 0.71wt% |
| Application Example 5 | 100 | 900 | 0.89wt% |
The surface migration sex flame retardant and polystyrene of Nitrogen-and Phosphorus-containing are well mixed；In addition double screw extruder, in machine
Under conditions of 200-220 DEG C of temperature of group, 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 flammabilities are carried out to the sample, as a result shown in table 2：
With above-mentioned according to desirable embodiment of the invention as enlightenment, by above-mentioned description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to its technical scope is determined according to right.
Claims (10)
1. the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing, it is characterised in that its structural formula is as follows：
2. the preparation method of the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing as claimed in claim 1, it is characterised in that including
Following steps：
(1) tricresyl phosphate (4- aminophenyls) ester and 3,5- difluoro pyridine -4- formaldehyde are heated in a solvent, after reaction terminates, is obtained
Reaction system containing intermediate product I；
(2) DOPO is added in the reaction system containing intermediate product I that step (1) is obtained and is heated, after reaction terminates, washed
Wash, 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 a kind of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that：It is described
The mol ratio of tricresyl phosphate (4- aminophenyls) ester and 3,5- difluoro pyridine -4- formaldehyde is 1 in step (1):3.
4. the preparation method of the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that：It is described
The reaction time is 7-12h in step (1).
5. the preparation method of the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that：It is described
Heating-up temperature is 70 DEG C in step (1).
6. the preparation method of the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that：It is described
Solvent is ethanol, DMF or DMSO in step (1).
7. the preparation method of the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that：It is described
The addition of solvent is the 6-12 of tricresyl phosphate (4- aminophenyls) ester and 3,5- difluoro pyridine -4- formaldehyde quality sums in step (1)
Times.
8. the preparation method of the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that：It is described
The mol ratio of the 3,5- difluoro pyridine -4- formaldehyde in the DOPO and step (1) in step (2) is 1:1.
9. the preparation method of the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that：It is described
Reaction temperature in step (2) is 70 DEG C.
10. the preparation method of the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that：Institute
The reaction time in step (2) is stated for 4-8h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710119856.4A CN106905369B (en) | 2017-03-02 | 2017-03-02 | A kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof |
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| CN201710119856.4A CN106905369B (en) | 2017-03-02 | 2017-03-02 | A kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof |
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| CN106905369A true CN106905369A (en) | 2017-06-30 |
| CN106905369B CN106905369B (en) | 2019-01-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109629024A (en) * | 2018-12-10 | 2019-04-16 | 天津工业大学 | Dendritic phosphorous-nitrogen system bittern-free fire retardant and its preparation method and application |
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2017
- 2017-03-02 CN CN201710119856.4A patent/CN106905369B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109629024A (en) * | 2018-12-10 | 2019-04-16 | 天津工业大学 | Dendritic phosphorous-nitrogen system bittern-free fire retardant and its preparation method and application |
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Effective date of registration: 20200131 Address after: 315400 No.7 Xingbin Road, Binhai New Town, Yuyao Economic Development Zone, Ningbo City, Zhejiang Province (former Binhai Industrial Park) Patentee after: Ningbo Hua Tan first research and new materials Co., Ltd. Address before: 215600 New Material Technology Development Co., Ltd. of Fangang Village, Yangshe Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee before: Five lakes new material technology development corporation, Ltd. of Zhangjagang City |
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