CN106928278A - A kind of new DOPO based flameproofings and preparation method thereof - Google Patents
A kind of new DOPO based flameproofings and preparation method thereof Download PDFInfo
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- CN106928278A CN106928278A CN201710119869.1A CN201710119869A CN106928278A CN 106928278 A CN106928278 A CN 106928278A CN 201710119869 A CN201710119869 A CN 201710119869A CN 106928278 A CN106928278 A CN 106928278A
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- new
- dopo
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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)
-
- 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
- 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
-
- 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 new DOPO based flameproofings, its structural formula is as follows：A kind of preparation method of new DOPO based flameproofings, comprises the following steps：(1) tricresyl phosphate (4 aminophenyl) ester and the trifluoro-methoxybenzaldehyde of 3 fluorine 5 are 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 new DOPO based flameproofings.A kind of new DOPO based flameproofings 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 new DOPO based flameproofings and preparation method thereof.
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 new DOPO based flameproofings and its preparation side
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%, solidification
Thing 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 new DOPO based flameproofings, its structural formula is as follows：
A kind of preparation method of new DOPO based flameproofings, comprises the following steps：
(1) tricresyl phosphate (4- aminophenyls) ester and the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- are heated in a solvent, reaction knot
Shu Hou, 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,
Wash, dry, obtain new DOPO based flameproofings.
Its course of reaction is：
Specifically, tricresyl phosphate (4- aminophenyls) ester and the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- rub in above-mentioned steps (1)
You are than being 1:3.
Specifically, the reaction time is 5-8h 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, the addition of solvent is tricresyl phosphate (4- aminophenyls) ester and the fluoro- 5- fluoroforms of 3- in above-mentioned steps (1)
5-10 times of epoxide benzaldehyde quality sum.
Specifically, the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- in the DOPO and step (1) in above-mentioned steps (2) mole
Than being 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 3-6h.
The device have the advantages that：
(1) a kind of new DOPO based flameproofings of the invention, with the increase of phosphorus content in solidfied material, solidfied material it is fire-retardant
Property increase；When flame retardant agent content reaches 5-10% (phosphorus content is 0.39wt%-0.78wt%), solidfied material can reach UL-
94, V-0 grades.
(2) a kind of new DOPO based flameproofings of the invention, introduce substantial amounts of fluorine element, can make fire retardant in solidification
There is certain surface migration, make the content of fire retardant in solidfied material gradually increases from inside to outside, makes solidfied material surface in thing
Highest containing flame retardant amount, makes that its addition is low, and flame retardant effect is excellent.
(3) a kind of new DOPO based flameproofings of the invention, although fluorine element is introduced on fire retardant, but due to C-
F keys can not effectively catch free radical very much by force, make fire retardant that there is excellent Thermal stability-Ultraviolet to irradiate, to light stabilizer
Function 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 new DOPO based flameproofings nuclear magnetic spectrogram 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 new DOPO based flameproofings is：
(1) by the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- of tricresyl phosphate (4- aminophenyls) ester of 9.3g and 19.5g at 70 DEG C
144g ethanol in heat 5h, after reaction terminates, obtain the reaction system containing intermediate product I；
(2) DOPO of 16.2g is added in the reaction system containing intermediate product I that step (1) is obtained in 70 DEG C of bars
3h heating under part, after reaction terminates, washs, dries, and obtains new DOPO based flameproofings, yield 86.6%.
Its infrared test result is as follows：
FTIR(KBr)：N-H stretching vibration peaks 3410cm-1, C-H stretching vibration peaks 3065cm-1, C-N characteristic peaks 1288cm-1, C-F characteristic peaks 1105cm-1, C-O-C characteristic peaks 1050cm-1, P-O-C characteristic peaks 1031cm-1, P-O-Ph characteristic peaks
1231cm-1, P-Ph characteristic peaks 1595cm-1, P=O characteristic peaks 1211cm-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 7.51 (m, 3H), 7.36 (l, 3H), 7.29-7.31 (k, 9H), 7.04-
7.05 (j, 9H), 6.88 (i, 3H), 6.79 (g, 3H), 6.51 (f, 6H), 6.34 (e, 3H), 6.29 (d, 3H), 6.26 (c, 6H),
4.01 (b, 3H), 3.91 (a, 3H).
Embodiment 2
A kind of synthesis step of new DOPO based flameproofings is：
(1) by the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- of tricresyl phosphate (4- aminophenyls) ester of 18.6g and 39g at 70 DEG C
460.9g DMF in heat 6.5h, after reaction terminates, obtain 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) is obtained in 70 DEG C of bars
4.5h heating under part, after reaction terminates, washs, dries, and obtains new DOPO based flameproofings, yield 87.1%.
Its infrared test result is as follows：
FTIR(KBr)：N-H stretching vibration peaks 3405cm-1, C-H stretching vibration peaks 3065cm-1, C-N characteristic peaks 1288cm-1, C-F characteristic peaks 1105cm-1, C-O-C characteristic peaks 1065cm-1, P-O-C characteristic peaks 1031cm-1, P-O-Ph characteristic peaks
1231cm-1, P-Ph characteristic peaks 1593cm-1, P=O characteristic peaks 1210cm-1, the out-of-plane bending vibration peak 850cm of fragrant hydrogen-1。
Embodiment 3
A kind of synthesis step of new DOPO based flameproofings is：
(1) by the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- of tricresyl phosphate (4- aminophenyls) ester of 27.8g and 58.5g 70
DEG C 863g DMF in heat 8h, after reaction terminates, obtain the reaction system containing intermediate product I；
(2) DOPO of 48.6g 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 new DOPO based flameproofings, yield 87.3%.
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 1287cm-1, C-F characteristic peaks 1105cm-1, C-O-C characteristic peaks 1055cm-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 1210cm-1, the out-of-plane bending vibration peak 850cm of fragrant hydrogen-1。
Application Example：
Material is weighed according to table 1：
Table 1：
| Application Example | New DOPO based flameproofings (g) | Polystyrene (g) | P content |
| Application Example 1 | 30 | 970 | 0.23wt% |
| Application Example 2 | 40 | 960 | 0.31wt% |
| Application Example 3 | 50 | 950 | 0.39wt% |
| Application Example 4 | 80 | 920 | 0.62wt% |
| Application Example 5 | 100 | 900 | 0.78wt% |
New DOPO based flameproofings and polystyrene are well mixed；In addition double screw extruder, in unit temperature
200-220 DEG C, 210 DEG C of die head temperature, under conditions of screw speed 200rpm, extruding pelletization, then through drying, cooling is hindered
Combustion 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. a kind of new DOPO based flameproofings, it is characterised in that its structural formula is as follows：
2. a kind of preparation method of new DOPO based flameproofings as claimed in claim 1, it is characterised in that comprise the following steps：
(1) tricresyl phosphate (4- aminophenyls) ester and the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- 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, washed
Wash, dry, obtain new DOPO based flameproofings.
3. a kind of preparation method of new DOPO based flameproofings as claimed in claim 2, it is characterised in that：The step (1)
The mol ratio of middle tricresyl phosphate (4- aminophenyls) ester and the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- is 1:3.
4. a kind of preparation method of new DOPO based flameproofings as claimed in claim 2, it is characterised in that：The step (1)
The middle reaction time is 5-8h.
5. a kind of preparation method of new DOPO based flameproofings as claimed in claim 2, it is characterised in that：The step (1)
Middle heating-up temperature is 70 DEG C.
6. a kind of preparation method of new DOPO based flameproofings as claimed in claim 2, it is characterised in that：The step (1)
Middle solvent is ethanol, DMF or DMSO.
7. a kind of preparation method of new DOPO based flameproofings as claimed in claim 2, it is characterised in that：The step (1)
The addition of middle solvent is 5-10 times of tricresyl phosphate (4- aminophenyls) ester and the fluoro- 5- trifluoro-methoxybenzaldehydes quality sums of 3-.
8. a kind of preparation method of new DOPO based flameproofings as claimed in claim 2, it is characterised in that：The step (2)
In DOPO and step (1) in the fluoro- 5- trifluoro-methoxybenzaldehydes of 3- mol ratio be 1:1.
9. a kind of preparation method of new DOPO based flameproofings as claimed in claim 2, it is characterised in that：The step (2)
In reaction temperature be 70 DEG C.
10. a kind of preparation method of new DOPO based flameproofings as claimed in claim 2, it is characterised in that：The step (2)
In reaction time be 3-6h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710119869.1A CN106928278A (en) | 2017-03-02 | 2017-03-02 | A kind of new DOPO based flameproofings and preparation method thereof |
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| CN201710119869.1A CN106928278A (en) | 2017-03-02 | 2017-03-02 | A kind of new DOPO based flameproofings and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628179A (en) * | 2019-08-30 | 2019-12-31 | 厦门大学 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
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|---|---|---|---|---|
| WO2011099461A1 (en) * | 2010-02-09 | 2011-08-18 | 丸菱油化工業株式会社 | Flame-retardant, and flame-retardant resin composition |
| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
-
2017
- 2017-03-02 CN CN201710119869.1A patent/CN106928278A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011099461A1 (en) * | 2010-02-09 | 2011-08-18 | 丸菱油化工業株式会社 | Flame-retardant, and flame-retardant resin composition |
| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
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| Title |
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| CORNELIU HAMCIUC等: ""Environmentally friendly fire-resistant epoxy resins based on a new oligophosphonate with high flame retardant efficiency"", 《RSC ADVANCES》 * |
| 钱立军 等编著: "《新型阻燃剂制造与应用》", 31 March 2013, 北京：化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628179A (en) * | 2019-08-30 | 2019-12-31 | 厦门大学 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
| CN110628179B (en) * | 2019-08-30 | 2020-11-17 | 厦门大学 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
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