CN106832408B - A kind of siliceous DOPO derivative flame retardant and preparation method thereof - Google Patents
A kind of siliceous DOPO derivative flame retardant and preparation method thereof Download PDFInfo
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- CN106832408B CN106832408B CN201710119969.4A CN201710119969A CN106832408B CN 106832408 B CN106832408 B CN 106832408B CN 201710119969 A CN201710119969 A CN 201710119969A CN 106832408 B CN106832408 B CN 106832408B
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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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
Abstract
The present invention relates to technical field of flame retardant, and in particular to a kind of siliceous DOPO derivative flame retardant, structural formula are as follows:A kind of preparation method of siliceous DOPO derivative flame retardant includes the following steps: (1) for amino dimethyl pentafluorophenyl group silane and 3, and 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 siliceous DOPO derivative flame retardant.A kind of siliceous DOPO derivative flame retardant 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 siliceous DOPO derivative flame retardant and its preparation side
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 siliceous DOPO derivative flame retardant 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 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 siliceous DOPO derivative flame retardant, structural formula are as follows:
A kind of preparation method of siliceous DOPO derivative flame retardant, includes the following steps:
(1) by amino dimethyl pentafluorophenyl group silane 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 siliceous DOPO derivative flame retardant.
Its reaction process are as follows:
Specifically, amino dimethyl pentafluorophenyl group silane and 3 in above-mentioned steps (1), mole of 5- difluoro pyridine -4- formaldehyde
Than for 1:1.
Specifically, the reaction time is 6-8h in above-mentioned steps (1).
Specifically, heating temperature is 75 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 amino dimethyl pentafluorophenyl group silane and 3,5- difluoro pyrrole in above-mentioned steps (1)
7-14 times of pyridine -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 75 DEG C.
Specifically, the reaction time in above-mentioned steps (2) is 4-6h.
The invention has the benefit that
(1) the siliceous DOPO derivative flame retardant of one kind of the invention, with the increase of phosphorus content in solidfied material, solidfied material
Anti-flammability increase；When flame retardant agent content reaches 5-10% (phosphorus content 0.26wt%-0.53wt%), solidfied material can reach
To UL-94, V-0 grades.
(2) the siliceous DOPO derivative flame retardant of one kind of the invention, introduces a large amount of fluorine element, can make fire retardant
There is certain surface migration in solidfied material, gradually increase the content of fire retardant in solidfied material from inside to outside, make to solidify
Object surface highest containing flame retardant amount, keeps its additive amount low, flame retardant effect is excellent.
(3) one kind of the invention siliceous DOPO derivative flame retardant contains fluorine atom in structure, since C-F key is too strong
And free radical cannot be effectively captured, make fire retardant that there is preferable thermal stability, ultraviolet radiation resisting acts on shadow to light stabilizer
Sound is 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 siliceous DOPO derivative flame retardant nuclear magnetic spectrogram 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 siliceous DOPO derivative flame retardant are as follows:
(1) by the 3,5- difluoro pyridine -4- formaldehyde of the amino dimethyl pentafluorophenyl group silane of 7.2g and 4.3g at 75 DEG C
6h is heated in 80.4g ethyl alcohol, after reaction, obtains the reaction system containing intermediate product I；
(2) DOPO of 6.5g is added in the reaction system containing intermediate product I that step (1) obtains in 75 DEG C of conditions
Lower 4h heating, after reaction, washing, drying obtain siliceous DOPO derivative flame retardant, yield 85.5%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3415cm-1, C-H stretching vibration peak 3080cm-1, C-N characteristic peak 1288cm-1, C-F characteristic peak 1100cm-1, C-Si characteristic peak 1255cm-1, P-O-C characteristic peak 1035cm-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 (k, 2H), 7.5 (j, 1H), 7.3-7.31 (i, 3H), 7.20 (g,
1H), 7.05 (f, 1H), 6.88 (e, 1H), 6.79 (d, 1H), 3.91 (c, 1H), 2.01 (b, 1H), 0.66 (a, 6H).
Embodiment 2
A kind of synthesis step of siliceous DOPO derivative flame retardant are as follows:
(1) by the 3,5- difluoro pyridine -4- formaldehyde of the amino dimethyl pentafluorophenyl group silane of 12.1g and 7.2g at 75 DEG C
7h is heated in 192.5g DMF, 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 75 DEG C of items
5h is heated under part, and after reaction, washing, drying obtain siliceous DOPO derivative flame retardant, yield 84.9%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3410cm-1, C-H stretching vibration peak 3070cm-1, C-N characteristic peak 1288cm-1, C-F characteristic peak 1100cm-1, C-Si characteristic peak 1250cm-1, P-O-C characteristic peak 1035cm-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 850cm of fragrant hydrogen-1。
Embodiment 3
A kind of synthesis step of siliceous DOPO derivative flame retardant are as follows:
(1) by the 3,5- difluoro pyridine -4- formaldehyde of the amino dimethyl pentafluorophenyl group silane of 24.1g and 14.3g at 75 DEG C
538g DMSO in heat 8h, after reaction, obtain the reaction system containing intermediate product I；
(2) DOPO of 21.6g is added in the reaction system containing intermediate product I that step (1) obtains in 75 DEG C of items
6h is heated under part, and after reaction, washing, drying obtain siliceous DOPO derivative flame retardant, yield 86.1%.
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 1288cm-1, C-F characteristic peak 1100cm-1, C-Si characteristic peak 1255cm-1, P-O-C characteristic peak 1038cm-1, P-O-Ph characteristic peak 1231cm-1, P-Ph characteristic peak 1595cm-1, P=O characteristic peak 1214cm-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 | Siliceous DOPO derivative flame retardant (g) | Polystyrene (g) | P content |
| Application Example 1 | 30 | 970 | 0.16wt% |
| Application Example 2 | 40 | 960 | 0.21wt% |
| Application Example 3 | 50 | 950 | 0.27wt% |
| Application Example 4 | 80 | 920 | 0.43wt% |
| Application Example 5 | 100 | 900 | 0.53wt% |
Siliceous DOPO derivative flame retardant and polystyrene are uniformly mixed；It adds twin-screw extrude, in unit
Under conditions of 200-220 DEG C of temperature, 210 DEG C of die head temperature, screw speed 200rpm, extruding pelletization, then through drying, cooling is obtained
To 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 siliceous DOPO derivative flame retardant, which is characterized in that its structural formula is as follows:
。
2. a kind of preparation method of siliceous DOPO derivative flame retardant as described in claim 1, it is characterised in that including such as
Lower step:
(1) by amino dimethyl pentafluorophenyl group silane and 3,5- difluoro pyridine -4- formaldehyde heats in a solvent, after reaction,
Obtain 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, washed
It washs, dry, obtain siliceous DOPO derivative flame retardant.
3. a kind of preparation method of siliceous DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: the step
Suddenly the molar ratio of amino dimethyl pentafluorophenyl group silane and 3,5- difluoro pyridine -4- formaldehyde is 1:1 in (1).
4. a kind of preparation method of siliceous DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: described
The reaction time is 6-8 h in step (1).
5. a kind of preparation method of siliceous DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: the step
Suddenly heating temperature is 75 DEG C in (1).
6. a kind of preparation method of siliceous DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: the step
Suddenly solvent is ethyl alcohol, DMF or DMSO in (1).
7. a kind of preparation method of siliceous DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: the step
Suddenly in (1) solvent additional amount be amino dimethyl pentafluorophenyl group silane and 3,5- difluoro pyridine -4- formaldehyde quality sum 7-14
Times.
8. a kind of preparation method of siliceous DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: the step
Suddenly the molar ratio of the 3,5- difluoro pyridine -4- formaldehyde in the DOPO in (2) and step (1) is 1:1.
9. a kind of preparation method of siliceous DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: the step
Suddenly the reaction temperature in (2) is 75 DEG C.
10. a kind of preparation method of siliceous DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: described
Reaction time in step (2) is 4-6 h.
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| CN101445520A (en) * | 2007-11-26 | 2009-06-03 | 中国科学院化学研究所 | Phosphoric organic silicon compound, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0559170A (en) * | 1991-08-30 | 1993-03-09 | Yoshio Imai | Method for producing polymide composition |
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2017
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| CN101445520A (en) * | 2007-11-26 | 2009-06-03 | 中国科学院化学研究所 | Phosphoric organic silicon compound, preparation method and application thereof |
| CN101792537A (en) * | 2010-03-17 | 2010-08-04 | 北京理工大学 | Silane coupling agent containing DOPO group and preparation method thereof |
| CN102206398A (en) * | 2011-03-28 | 2011-10-05 | 中国科学院化学研究所 | Liquid epoxy underfill, preparation method and application thereof |
| CN103073749A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Preparation method and application of nano composite flame retardant containing DOPO and delamination graphene |
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| Preparation and properties of halogen-free flame retardant epoxy resins with phosphorus-containing siloxanes;Jiapei Ding,et al.;《Polymer Bulletin》;20070630;第829-841页 |
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