CN106905369B - 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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- CN106905369B CN106905369B CN201710119856.4A CN201710119856A CN106905369B CN 106905369 B CN106905369 B CN 106905369B CN 201710119856 A CN201710119856 A CN 201710119856A CN 106905369 B CN106905369 B CN 106905369B
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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, structural formula are as follows:A kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, include the following steps: (1) by tricresyl phosphate (4- aminophenyl) ester and 3,5- difluoro pyridine -4- formaldehyde heats in a solvent, after reaction, obtains the 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.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.
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-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of Nitrogen-and Phosphorus-containing surface migration sex flame retardant and
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 achieve UL94, and V-0 grades.
To achieve the purpose of the present invention, the present invention adopts the following technical scheme:
A kind of surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, structural formula are as follows:
A kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing, includes the following steps:
(1) by tricresyl phosphate (4- aminophenyl) ester and 3,5- difluoro pyridine -4- formaldehyde heats in a solvent, and 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) 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:
Specifically, tricresyl phosphate (4- aminophenyl) ester and 3 in above-mentioned steps (1), the molar ratio of 5- difluoro pyridine -4- formaldehyde
For 1:3.
Specifically, the reaction time is 7-12h in above-mentioned steps (1).
Specifically, heating temperature is 70 DEG C in above-mentioned steps (1).
Specifically, solvent is ethyl alcohol, DMF or DMSO in above-mentioned steps (1).
Specifically, the additional amount of solvent is tricresyl phosphate (4- aminophenyl) ester and 3,5- difluoro pyridine-in above-mentioned steps (1)
6-12 times of 4- formaldehyde quality sum.
Specifically, the molar 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 invention has the benefit 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 0.44wt%-0.89wt%), solidfied material can be with
Reach UL-94, V-0 grades.
(2) there is the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing of the invention high flame retardant, low cigarette, low toxicity to do harm to, without corruption
Corrosion gas generates.
(3) the surface migration sex flame retardant of a kind of Nitrogen-and Phosphorus-containing of the invention contains fluorine atom in structure, too due to C-F key
Free radical cannot be effectively captured by force, makes fire retardant that there is preferable thermal stability, ultraviolet radiation resisting acts on light stabilizer
It influences small.
(4) raw material used in the present invention is easy to get, is simple process, at low cost, easy to industrialized production.
Detailed description of the invention
Present invention will be further explained below with reference to the attached 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 described in further detail.
Embodiment 1
A kind of synthesis step of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing are as follows:
(1) by the 3,5- difluoro pyridine -4- formaldehyde of the tricresyl phosphate of 11.1g (4- aminophenyl) ester and 12.9g at 70 DEG C
7h is heated in 144g ethyl alcohol, after reaction, obtains the reaction system containing intermediate product I；
(2) DOPO of 19.5g is added in the reaction system containing intermediate product I that step (1) obtains in 70 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 84.9%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3410cm-1, C-H stretching vibration peak 3075cm-1, C-N characteristic peak 1289cm-1, C-F characteristic peak 1100cm-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, the out-of-plane bending vibration peak 900cm of fragrant hydrogen-1。
Nuclear magnetic spectrogram 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 are as follows:
(1) by the 3,5- difluoro pyridine -4- formaldehyde of the tricresyl phosphate of 18.6g (4- aminophenyl) ester and 21.5g at 70 DEG C
10h is heated in 401g DMF, after reaction, obtains the reaction system containing intermediate product I；
(2) DOPO of 32.4g is added in the reaction system containing intermediate product I that step (1) obtains in 70 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 84.8%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3415cm-1, C-H stretching vibration peak 3075cm-1, C-N characteristic peak 1289cm-1, C-F characteristic peak 1100cm-1, P-O-C characteristic peak 1033cm-1, P-O-Ph characteristic peak 1231cm-1, P-Ph characteristic peak 1590cm-1, P=O characteristic peak 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 are as follows:
(1) by the 3,5- difluoro pyridine -4- formaldehyde of the tricresyl phosphate of 37.1g (4- aminophenyl) ester and 42.9g at 70 DEG C
12h is heated in 960g DMSO, after reaction, obtains the reaction system containing intermediate product I；
(2) DOPO of 64.9g is added in the reaction system containing intermediate product I that step (1) obtains in 70 DEG C of items
8h is heated under part, and after reaction, washing, drying obtain 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 peak 3420cm-1, C-H stretching vibration peak 3080cm-1, C-N characteristic peak 1288cm-1, C-F characteristic peak 1100cm-1, P-O-C characteristic peak 1033cm-1, P-O-Ph characteristic peak 1231cm-1, P-Ph characteristic peak 1590cm-1, P=O characteristic peak 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 | The 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 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:
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above 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 range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
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 as described in claim 1, it is characterised in that including
Following steps:
(1) by tricresyl phosphate (4- aminophenyl) ester and 3,5- difluoro pyridine -4- formaldehyde is 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, washed
It washs, dry, obtain the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing.
3. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that: described
The molar ratio of tricresyl phosphate (4- aminophenyl) ester and 3,5- difluoro pyridine -4- formaldehyde is 1:3 in step (1).
4. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that: described
The reaction time is 7-12 h in step (1).
5. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that: described
Heating temperature is 70 DEG C in step (1).
6. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that: described
Solvent is ethyl alcohol, DMF or DMSO in step (1).
7. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that: described
The additional amount of solvent is the 6-12 of tricresyl phosphate (4- aminophenyl) ester and 3,5- difluoro pyridine -4- formaldehyde quality sum in step (1)
Times.
8. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that: described
The molar ratio of 3,5- difluoro pyridine -4- formaldehyde in DOPO and step (1) in step (2) is 1:1.
9. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that: described
Reaction temperature in step (2) is 70 DEG C.
10. a kind of preparation method of the surface migration sex flame retardant of Nitrogen-and Phosphorus-containing as claimed in claim 2, it is characterised in that: institute
Stating the reaction time in step (2) is 4-8 h.
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| CN106905369B true CN106905369B (en) | 2019-01-15 |
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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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