CN106916337A - Antimony oxide loads bromination Graphene fire retardant - Google Patents
Antimony oxide loads bromination Graphene fire retardant Download PDFInfo
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- CN106916337A CN106916337A CN201510559315.4A CN201510559315A CN106916337A CN 106916337 A CN106916337 A CN 106916337A CN 201510559315 A CN201510559315 A CN 201510559315A CN 106916337 A CN106916337 A CN 106916337A
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- antimony oxide
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Abstract
The invention discloses a kind of antimony oxide load bromination Graphene fire retardant and application thereof, its composition contains bromination Graphene and antimony oxide powder particle, antimony oxide powder particle is grafted on bromination Graphene by chemical bond, wherein bromo element has certain mass content respectively with antimony oxide, under this mass content, the performance of fire retardant is optimal.The features such as fire retardant that the present invention is provided has environmentally friendly, applied widely, good flame retardation effect, stable performance and can preferably disperse in polymeric matrix, especially the characteristics of environmental protection, greatly solves the problems, such as the secondary pollution of halogenated flame retardant.Application the invention discloses it in flame retarded polymeric material is prepared.
Description
Technical field
The present invention relates to a kind of fire retardant, and in particular to a kind of antimony oxide loads bromination Graphene fire retardant, especially its
Application in flame retarded polymeric material is prepared.
Background technology
Fire retardant is the functionalization auxiliary agent for referring to improve inflammable or combustible flame retardancy, self-extinguishment or smoke elimination.According to
Chemical constitution, fire retardant can be divided into inorganic and organic two class again, wherein organic fire-retardant can be further subdivided into halogen system, phosphorus system,
Halogen-phosphorus system, phosphorus-nitrogen system, silicon systems etc.；And inorganic combustion inhibitor generally comprises magnalium system, antimony system, boron system, Phos system, molybdenum system
Deng.
Current fire retardant main market players is occupied by inorganic fire-retarded system and halogen-antimony flame-retardant system.Aluminium hydroxide etc. is inorganic
Fire retardant addition is higher, so causes material mechanical performance to decline to a great extent, and limits it and uses scope.Halogen-antimony flame-retardant system is (special
It is not bromo- antimony flame-retardant system) there is good flame retardation effect, consumption is few, the advantages of the Effect on Mechanical Properties to material is small, for a long time
Used as main fire-retardant kind always.But halogenated flame retardant (such as decabromodiphenyl oxide) easily causes " two in use
Secondary harm " and pollute environment, urgent need finds a kind of new halide instead of decabromodiphenyl oxide etc., solves current halogenated flame retardant
The challenge being faced with.
It is reported that add Graphene in traditional flame-retardant system, the consumption of conventional flame retardant can be reduced, Graphene with
Conventional flame retardant has cooperative effect, and both and use can improve the fire resistance of material.Graphene is the tightly packed Cheng Dan of carbon atom
A kind of carbonaceous new material of layer bi-dimensional cellular shape lattice structure, with characteristics such as high intensity, high conductivity and high-specific surface areas.But
Graphene is used alone, its fire-retardant rank is relatively low seriously to be limited it and use scope.And this mixed system is at present simply by both
Simple physical blending is obtained, and Graphene and fire retardant are difficult to realize dispersed in polymeric matrix, have a strong impact in material
The performance of both cooperative flame retardant effects in combustion process.
The weak point of current halogenated flame retardant is summarized as：1st, poisonous cigarette, gas are easily released in use, it is dirty
Dye human body and environment；2nd, at present with other fire retardant cooperative flame retardants, in polymeric matrix be difficult to realize dispersed, serious shadow
Ring the performance of both cooperative flame retardant effects during material combustion.
The content of the invention
First purpose of the invention is to provide a kind of new fire retardant, specifically a kind of antimony oxide load bromination graphite
Alkene fire retardant, structural formula such as formula (1)：
Its composition contains bromination Graphene and antimony oxide powder particle, and antimony oxide powder particle is grafted on bromination by chemical bond
On Graphene.
The present invention attempts that fire retardant is grafted into graphenic surface by chemical reaction, and a kind of functionalization graphene base resistance is obtained
Combustion agent, can not only improve dispersiveness and the mechanical property of material of the Graphene in polymeric matrix, and can significantly increase fire-retardant
Agent is acted on Graphene cooperative flame retardant, for the high performance for realizing halogen system fire proofing provides possibility.The present invention passes through experiment,
This imagination is demonstrated, from the preferable bromo- sb system of performance as research object, ignition-proof element bromine, antimony is supported on respectively
On Graphene, antimony oxide load bromination Graphene fire retardant has been obtained.
Antimony oxide of the invention loads bromination Graphene fire retardant, with following property：
(1) mass content of its bromo element is 1~25%, and the mass content of antimony oxide is 1~40%；
(2) wherein the particle diameter of antimony oxide particle is 10~400 nanometers.
(3) density is 1.1~2.9g/cm3；
(4) hot initial decomposition temperature is 250~350 DEG C；
(5) water insoluble, organic solvent, acid, alkali.
The present invention is graphene oxide from Graphene, is one because graphene oxide is used as the important derivatives of Graphene
The new carbon of excellent performance is planted, with higherSpecific surface areaAbundant with surfaceFunctional group, for the load of bromo element is provided
Possibility.What antimony oxide particle was selected is nanoscale, and used as fire retarding synergist, the stretching and impact that can improve material are strong
Degree physicochemical property.What bromine source was selected is bromine, and simple and easy to get, price is relatively cheap, and bromine can directly and graphene oxide
Reaction, so that bromo element is supported on Graphene, it is difficult for drop-off.Bromo element and antimony oxide can make under this mass content
The performance of fire retardant is to optimal, and mass content is too high undoubtedly also improves cost, is not suitable for so.
To obtain above-mentioned antimony oxide load bromination Graphene fire retardant, the technical scheme of use is summarized as follows：
(1) antimony oxide powder particle reacts with the silane coupler of amino-contained, then carries out surface with graphene oxide again and connects
Branch reaction, is obtained antimony oxide grafted graphene oxide.
(2) above-mentioned antimony oxide grafted graphene oxide is obtained antimony oxide grafting bromination Graphene by bromination reaction.
(3) above-mentioned antimony oxide grafting bromination Graphene is obtained described antimony oxide load bromination stone by reduction reaction
Black alkene fire retardant.
The antimony oxide loads bromination Graphene fire retardant, can apply to flame-retardant high-molecular polymeric material.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects：
(1) antimony oxide load bromination Graphene fire retardant of the present invention, the table of Graphene is anchored at due to bromo element
Face, it is difficult for drop-off, its toxicity and the harm to environment can be substantially reduced in use；
(2) ignition-proof element bromine, antimony are supported on graphenic surface, make new fire retardant while having three kinds of ignition-proof elements, in polymer
Three kinds of ignition-proof elements of fire retardant can be realized dispersed in matrix, solve dispersion problem of the fire retardant in macromolecular material,
Improve flame retardant effect of the fire retardant to polymer；
(3) fire retardant of the present invention is acted on using bromide with antimony oxide cooperative flame retardant, is improved to macromolecular material
Flame retardant effect, reduces usage amount of the fire retardant in macromolecular material, reduces the cost of fire proofing；The addition of Graphene, to poly-
Compound matrix has humidification, for example, enhance electric conductivity, improves the mechanical property of fire proofing.
Fire retardant of the present invention is environment-friendly and low-toxicity, addition is low, good flame retardation effect, applied widely, and in macromolecule
There is good dispersiveness in polymer.Especially the characteristics of environmental protection, the secondary pollution of halogenated flame retardant is greatly solved the problems, such as.
Brief description of the drawings
Fig. 1 is antimony oxide load bromination Graphene infrared spectrogram
Fig. 2 is antimony oxide load bromination Graphene xps energy spectrum figure
Fig. 3 is antimony oxide load bromination Graphene TEM figures
Specific embodiment
Product of the invention and application, but protection scope of the present invention not limited to this are illustrated with specific embodiment below.
Embodiment 1：Prepare antimony oxide load bromination Graphene fire retardant
4.5g antimony oxide powder particles are added in 150mL toluene, ultrasonic disperse is moved into anti-after 30 minutes
Answer in bottle, 0.5g gamma-aminopropyl-triethoxy-silanes and 10mL toluene mixture liquids be added dropwise under normal temperature, be refluxed reaction 6 hours,
Then reacting slurry is filtered, is washed, in 80 DEG C of dryings, obtain final product organic modification antimony oxide.
The above-mentioned reactions of 0.4g are obtained organic modification antimony oxide, 1.6g graphene oxides, 250mL second is added to
In acetoacetic ester, after the minor clock of ultrasonic disperse 2, reaction bulb is moved into, add 0.2g dicyclohexylcarbodiimides, 55 DEG C of stirrings
The slurries that reaction is obtained, are then filtrated to get black solid powder by reaction 10 hours, are washed with methyl alcohol, in 60 DEG C of dryings,
Obtain final product antimony oxide load graphene oxide.
The above-mentioned reactions of 1g are obtained into antimony oxide load graphene oxide to be placed in the closed container containing 35ml bromines, instead
Answer 72 hours, solid powder is taken out, with sodium carbonate liquor and distillation water washing solid powder, in 60 DEG C of dryings, obtain final product three
Aoxidize two antimony load bromination graphene oxide.
The above-mentioned reactions of 1g are obtained into antimony oxide load bromination graphene oxide to be added in 200mL distilled water, ultrasound point
After dissipating 2 minor clocks, reaction bulb is moved into, (quality is dense for dropwise addition 0.8mL hydrazine hydrates (mass concentration is 80%) and 3.5mL ammoniacal liquor
Spend for 28%), 60 DEG C of stirring reactions 4 hours, the suspension filtering that then reaction is obtained obtains solid powder, uses distilled water
Cyclic washing, in 60 DEG C of dryings 48 hours, obtains final product antimony oxide load bromination Graphene fire retardant, measures the fire retardant bromine
Mass content be 4.2%, the mass content of antimony oxide is 18.7%.
Structure determination is carried out to above-mentioned antimony oxide load bromination Graphene：Infrared test result is shown in Fig. 1；Xps energy spectrum (X
X-ray photoelectron spectroscopy X) see Fig. 2；TEM (transmission electron microscope) figure is shown in Fig. 3.
Embodiment 2：Antimony oxide loads the application of bromination Graphene fire retardant
The preparation manipulation of antimony oxide load bromination Graphene fire retardant is with embodiment 1.By 970g polyurethane elastomers and
30g antimony oxides load bromination Graphene fire retardant is put into high speed dispersor and stirs 10 minutes, by said mixture after taking-up,
By double screw extruder (processing temperature scope is 190~220 DEG C) extruding pelletization, polyurethane/antimony oxide load bromine is obtained
Graphite alkene composite, the result that cone calorimetry measures the fire-retardant performance of the composite is as shown in table 1.
1 polyurethane of table/antimony oxide load bromination graphene composite material and pure polyurethane flame-proof performance comparison
Embodiment 3：Antimony oxide loads the application of bromination Graphene fire retardant
The preparation manipulation of antimony oxide load bromination Graphene fire retardant is with embodiment 1.980g ethene-vinyl acetates are total to
Polymers (EVA) and 20g antimony oxides load bromination Graphene fire retardant are put into high speed dispersor and stir 8 minutes, will after taking-up
Said mixture, by double screw extruder (processing temperature scope is 130~150 DEG C) extruding pelletization, obtains the oxidations of EVA/ tri-
Two antimony load bromination Graphene fire retardant composite, and cone calorimetry measures the result such as institute of table 2 of the fire-retardant performance of the composite
Show.
The pure EVA/ antimony oxides load bromination graphene composite material of table 2 is contrasted with pure EVA fire resistances
By the Application Example 2,3 of the fire retardant as can be seen that antimony oxide loads bromination Graphene and polyphosphazene polymer
The composite of compound, has all been lifted, good flame retardation effect relative to macromolecular material sheet in every fire resistance.Also illustrate
Application of the antimony oxide load bromination Graphene fire retardant of the invention in flame retarded polymeric material is effective and feasible.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to this hair
The restriction of bright implementation method.For those of ordinary skill in the field, can also make on the basis of the above description
The change or variation of other multi-forms.Here all of implementation method cannot be exhaustive.It is every to belong to skill of the invention
Obvious change that art scheme is extended out changes row still in protection scope of the present invention.
Claims (5)
1. a kind of antimony oxide loads bromination Graphene fire retardant, it is characterised in that shown in its structure such as formula (1)：
Wherein, sheet carbon structure represents Graphene, and round represents antimony oxide particle.The fire retardant contains bromination Graphene
With antimony oxide powder particle, antimony oxide powder particle is grafted on bromination Graphene by chemical bond.
2. antimony oxide as claimed in claim 1 load bromination Graphene fire retardant, it is characterised in that wherein bromo element
Mass content is 1~25%, and the mass content of antimony oxide is 1~40%.
3. antimony oxide as claimed in claim 1 loads bromination Graphene fire retardant, it is characterised in that the heat of the fire retardant
Initial decomposition temperature is 250~350 DEG C.
4. antimony oxide as claimed in claim 1 load bromination Graphene fire retardant, it is characterised in that the fire retardant it is close
It is 1.1~2.9g/cm to spend3。
5. any antimony oxide loads bromination Graphene fire retardant in flame-retardant high-molecular polymeric material in Claims 1 to 4
Using.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181207A (en) * | 2018-09-29 | 2019-01-11 | 台州学院 | A kind of molybdenum-antimony bromination graphene oxide modified ABS composite flame-proof material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185144A (en) * | 2011-04-02 | 2011-09-14 | 浙江大学 | Metal oxide/graphene composite material and preparation method thereof |
| CN103819597A (en) * | 2014-02-19 | 2014-05-28 | 哈尔滨工业大学 | Preparation method of graphene containing expandable polystyrene polymer |
-
2015
- 2015-12-27 CN CN201510559315.4A patent/CN106916337A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185144A (en) * | 2011-04-02 | 2011-09-14 | 浙江大学 | Metal oxide/graphene composite material and preparation method thereof |
| CN103819597A (en) * | 2014-02-19 | 2014-05-28 | 哈尔滨工业大学 | Preparation method of graphene containing expandable polystyrene polymer |
Non-Patent Citations (2)
| Title |
|---|
| GUOBO HUANG ET AL: "Fabrication of multifunctional graphene decorated with bromine and nano-Sb2O3 towards high-performance polymer nanocomposites", 《CARBON》 * |
| 屈凌波: "《新型功能材料设计及应用》", 31 May 2014 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181207A (en) * | 2018-09-29 | 2019-01-11 | 台州学院 | A kind of molybdenum-antimony bromination graphene oxide modified ABS composite flame-proof material and preparation method thereof |
| CN109181207B (en) * | 2018-09-29 | 2021-01-29 | 台州学院 | Molybdenum-antimony brominated graphene oxide modified ABS composite flame-retardant material and preparation method thereof |
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Application publication date: 20170704 |