CN108440788B - A kind of preparation method of containing phosphorus silicon functional graphene oxide - Google Patents
A kind of preparation method of containing phosphorus silicon functional graphene oxide Download PDFInfo
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- CN108440788B CN108440788B CN201810213585.3A CN201810213585A CN108440788B CN 108440788 B CN108440788 B CN 108440788B CN 201810213585 A CN201810213585 A CN 201810213585A CN 108440788 B CN108440788 B CN 108440788B
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
The invention discloses a kind of preparation methods of containing phosphorus silicon functional graphene oxide.The present invention makes two N-H keys on gamma-aminopropyl-triethoxy-silane while connecting DOPO using succinct convenient experimental method, the phosphorous silicon element compound of one-step synthesis.The present invention is modified graphene using phosphorous silicon element compound, is expected to improve the dispersibility of graphene in organic solvent, and compatibility in the epoxy.Phosphorus, silicon ignition-proof element are introduced graphene oxide synthesized micromolecule fire retardant by the present invention, and the synergistic effect of the two facilitates the formation of coke layer, are expected to improve the thermal stability of epoxy resin.Reaction condition of the present invention is mild, and is free of halogen, is environmentally friendly new flame retardant.
Description
Technical field
The invention belongs to graphene technical field of modification, functional graphene oxide is specifically related to a kind of containing phosphorus silicon functionalization
The preparation method use of graphene oxide,.
Background technique
Graphene because its unique two-dimensional slice structure, high thermal stability, up to 1000GPa Young's modulus and
125GPa breaking strength has the effect of therefore good fire-retardant and toughening has tempting application in applied fireproofing field
Prospect.However, the interaction between graphene sheet layer is strong, dispersibility in organic solvent is poor, and preparation is caused to polymerize
Reunion is easy to happen when object nanocomposite, it is naturally not high with the compatibility of epoxy resin.It is therefore desirable to be carried out to graphene
It is modified, not only effectively piece interlayer was inhibited to reunite, but also certain cooperative flame retardant effect can be played.
Phosphorus-containing compound is current most widely used fire retardant, plays the gentle mutually fire-retardant effect of condensed phase, common
Have phosphate, phosphoric-oxygenic compound and organic phosphorus compound etc..Liao et al. passes through on the P-H key and graphene oxide on DOPO
Epoxy group occur ring-opening reaction, prepare the modified GO of DOPO, although its flame retardant property increases, increase rate compared with
Low, LOI comparison improves 13% when only adding GO.
Silicon-series five-retardant greatly inhibits asphalt mixtures modified by epoxy resin by forming layer of charcoal in condensed phase and capturing the free radical in gas phase
The flammability of the matrixes such as rouge common are caged silsesquioxane (POSS) and its derivative, polysiloxanes and inorganic silicon etc..
Wang et al. directly forms covalent bond using OapPOSS and graphene oxide, and applies it to epoxy resin, the results showed that
When the additive amount of OapPOSS-rGO is 2wt%, thermal degradation temperature is significant increases 43 DEG C for epoxy resin composite material starting, always
Heat liberation unit also reduces 58% than the maximum of pure epoxy, however OapPOSS is expensive is not appropriate for industrial application.
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of preparation of containing phosphorus silicon functional graphene oxide is provided
Method.
Technical scheme is as follows:
A kind of preparation method of containing phosphorus silicon functional graphene oxide, structural formula are as follows:
Specifically comprise the following steps:
(1) under nitrogen protection, under the action of the first solvent and paraformaldehyde, by the miscellaneous -10- phospha of 9,10- dihydro-9-oxy
P-H key on phenanthrene -10- oxide is reacted with the amino on gamma-aminopropyl-triethoxy-silane, and reaction temperature is 50~80
DEG C, phosphorous silicon element compound, molecule are obtained after then purifying by precipitating, decompression suction filtration and drying to reaction product
Structural formula are as follows:
The dosage of above-mentioned first solvent is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, three ethoxy of γ-aminopropyl
5~30 times of the gross mass of base silane and paraformaldehyde；Above-mentioned gamma-aminopropyl-triethoxy-silane, 9,10- dihydro-9-oxy be miscellaneous-
The molar ratio of 10- phospho hetero phenanthrene -10- oxide and paraformaldehyde is 1: 2~20: 2~10；
(2) it after being ultrasonically treated graphene oxide in the second solvent, is added with above-mentioned phosphorous after the dilution of third solvent
Reaction is hydrolyzed in 75~100 DEG C in silicon element compound, after then purifying by centrifugation and freeze-drying, obtains the containing phosphorus silicon
Functional graphene oxide；The mass ratio of above-mentioned graphene oxide and phosphorous silicon element compound is 1: 10~50.
In a preferred embodiment of the invention, first solvent includes dehydrated alcohol, carbon tetrachloride and trichlorine
Methane.
In a preferred embodiment of the invention, second solvent is dehydrated alcohol, n,N-Dimethylformamide
Or the mixed solvent of acetone and deionized water composition.
In a preferred embodiment of the invention, the third solvent includes dehydrated alcohol, toluene and acetone.
In a preferred embodiment of the invention, the time of the ultrasonic treatment is 30~60min.
In a preferred embodiment of the invention, the temperature of the hydrolysis is 78~100 DEG C of functionalization oxidations
Graphene the beneficial effects of the present invention are:
1, the present invention keeps two N-H keys on gamma-aminopropyl-triethoxy-silane same using succinct convenient experimental method
When connect DOPO, the phosphorous silicon element compound of one-step synthesis.
2, the present invention is modified graphene using phosphorous silicon element compound, is expected to improve graphene in organic solvent
In dispersibility, and compatibility in the epoxy.
3, phosphorus, silicon ignition-proof element are introduced graphene oxide synthesized micromolecule fire retardant, the synergistic effect of the two by the present invention
The formation for facilitating coke layer is expected to improve the thermal stability of epoxy resin.
4, reaction condition of the present invention is mild, and is free of halogen, is environmentally friendly new flame retardant.
Detailed description of the invention:
Fig. 1 is the infrared spectrum (IR) that the embodiment of the present invention 1 prepares resulting phosphorous silicon element compound.It is horizontal in Fig. 1
Coordinate is wave number Wavenumbers (cm-1), the infrared spectrum of APTS-bisDOPO is shown on gamma-aminopropyl-triethoxy-silane
Amino and DOPO on P-H key all disappear, there is the characteristic peak on the DOPO such as P=O, P-O-Ph, show successfully to synthesize phosphorous
Silicon element compound.
Fig. 2 is the infrared spectrum (IR) that the embodiment of the present invention 2 prepares resulting containing phosphorus silicon functional graphene oxide.Scheming
In 2, abscissa is wave number Wavenumbers (cm-1), the graphene oxide hydroxyl peak after function weakens, and DOPO occurs and should have
Characteristic peak, show successfully to synthesize containing phosphorus silicon functional graphene oxide.
Fig. 3 is the X-ray diffraction spectrogram that the embodiment of the present invention 2 prepares resulting containing phosphorus silicon functional graphene oxide
(XRD).In Fig. 3, abscissa is 2Theta angle, can obviously be obtained by contrast, the graphene oxide after function is at 22.6 ° or so
There is broad peak, and obviously weaken in 10 ° or so of peak intensity, this is attributed to is grafted one layer with the resistance of phosphorus silicon in surface of graphene oxide
Fire the small molecule of element.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
Embodiment 1
(1) 2.27g 9,10- dihydro-9-oxy is added in the reaction vessel of 50mL in the synthesis of phosphorous silicon element compound
Miscellaneous -10- phospho hetero phenanthrene -10- oxide, 1.11g gamma-aminopropyl-triethoxy-silane and 0.32g paraformaldehyde are dissolved in the three of 30mL
In chloromethanes, under nitrogen protection, it is stirred to react for 24 hours in 60 DEG C of reaction temperatures.Reaction solution sinks in n-hexane after reaction
It forms sediment and purifies, obtain phosphorous silicon element compound as shown in Figure 1.
(2) synthesis of containing phosphorus silicon functional graphene oxide
20mg graphene oxide is dissolved in 10mL deionized water and 40mL dehydrated alcohol mixed solution, after ultrasonic 60min,
Enter dropwise and is stirred to react for 24 hours at 78 DEG C with the phosphorous silicon element compound of 0.34g after 10mL dilution with toluene.After reaction
The containing phosphorus silicon functionalization is obtained after then purifying by centrifugation and freeze-drying with dehydrated alcohol, the multiple washed product of deionized water
Graphene oxide.
Embodiment 2
(1) synthesis of phosphorous silicon element compound
In the reaction vessel of 50mL, addition 2.27g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
1.11g gamma-aminopropyl-triethoxy-silane and 0.56g paraformaldehyde are dissolved in the carbon tetrachloride of 30mL, under nitrogen protection, 60
It is stirred to react for 24 hours in DEG C reaction temperature.Reaction solution precipitation purification in n-hexane after reaction.
(2) synthesis of containing phosphorus silicon functional graphene oxide
50mg graphene oxide is dissolved in 10mL deionized water and 40mLN, in dinethylformamide mixed solution, ultrasound
After 60min, enters be stirred to react for 24 hours at 78 DEG C with the phosphorous silicon element compound of 0.25g after 10mL dilution with toluene dropwise.Instead
Dehydrated alcohol, the multiple washed product of deionized water are used after answering, then by centrifugation and freeze-drying purification after, obtain such as Fig. 2 and
The containing phosphorus silicon functional graphene oxide shown in Fig. 3.
Embodiment 3
(1) synthesis of phosphorous silicon element compound
In the reaction vessel of 50mL, addition 3.14g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
1.52g gamma-aminopropyl-triethoxy-silane and 0.65g paraformaldehyde are dissolved in the chloroform of 30mL, under nitrogen protection, 60
It is stirred to react for 24 hours in DEG C reaction temperature.Reaction solution precipitation purification in n-hexane after reaction.
(2) synthesis of containing phosphorus silicon functional graphene oxide
80mg graphene oxide is dissolved in 10mL deionized water and 80mL dehydrated alcohol mixed solution, after ultrasonic 60min,
Enter dropwise and is stirred to react for 24 hours at 80 DEG C with the phosphorous silicon element compound of 0.25g after 10mL dilution with toluene.After reaction
The containing phosphorus silicon functionalization is obtained after then purifying by centrifugation and freeze-drying with dehydrated alcohol, the multiple washed product of deionized water
Graphene oxide.
Skilled person will appreciate that when parameter of the present invention changes in following ranges, it is contemplated that obtain and above-mentioned implementation
The same or similar technical effect of example, still falls within protection scope of the present invention:
A kind of preparation method of containing phosphorus silicon functional graphene oxide, structural formula are as follows:
Specifically comprise the following steps:
(1) under the action of the first solvent and paraformaldehyde, the miscellaneous -10- phospho hetero phenanthrene -10- of 9,10- dihydro-9-oxy is aoxidized
P-H key on object is reacted with the amino on gamma-aminopropyl-triethoxy-silane, and reaction temperature is 50~80 DEG C, is then led to
It crosses after precipitating, decompression suction filtration and drying purify reaction product and obtains phosphorous silicon element compound, molecular structural formula are as follows:
The dosage of above-mentioned first solvent is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, three ethoxy of γ-aminopropyl
5~30 times of the gross mass of base silane and paraformaldehyde；Above-mentioned gamma-aminopropyl-triethoxy-silane, 9,10- dihydro-9-oxy be miscellaneous-
The molar ratio of 10- phospho hetero phenanthrene -10- oxide and paraformaldehyde is 1: 2~20: 2~10；
(2) it after being ultrasonically treated graphene oxide in the second solvent, is added with above-mentioned phosphorous after the dilution of third solvent
Reaction is hydrolyzed in 75~100 DEG C in silicon element compound, after then purifying by centrifugation and freeze-drying, obtains the containing phosphorus silicon
Functional graphene oxide；The mass ratio of above-mentioned graphene oxide and phosphorous silicon element compound is 1: 10~50.
First solvent includes dehydrated alcohol, carbon tetrachloride and chloroform.Second solvent be dehydrated alcohol, N,
The mixed solvent of dinethylformamide or acetone and deionized water composition.The third solvent include dehydrated alcohol, toluene and
Acetone.The time of the ultrasonic treatment is 30~60min.The temperature of the hydrolysis is preferably 78~100 DEG C.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (3)
1. a kind of preparation method of containing phosphorus silicon functional graphene oxide, it is characterised in that:
Its structural formula are as follows:
Specifically comprise the following steps:
(1) under nitrogen protection, under the action of the first solvent and paraformaldehyde, by the miscellaneous -10- phospho hetero phenanthrene-of 9,10- dihydro-9-oxy
P-H key on 10- oxide is reacted with the amino on gamma-aminopropyl-triethoxy-silane, and reaction temperature is 50~80 DEG C,
Then phosphorous silicon element compound, molecule knot are obtained after purifying by precipitating, decompression suction filtration and drying to reaction product
Structure formula are as follows:
The dosage of above-mentioned first solvent is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, three ethoxy of γ-aminopropyl
5~30 times of the gross mass of base silane and paraformaldehyde；Above-mentioned gamma-aminopropyl-triethoxy-silane, 9,10- dihydro-9-oxy be miscellaneous-
The molar ratio of 10- phospho hetero phenanthrene -10- oxide and paraformaldehyde is 1: 2~20: 2~10；
(2) it after being ultrasonically treated graphene oxide in the second solvent, is added with the above-mentioned containing phosphorus silicon member after the dilution of third solvent
Reaction is hydrolyzed in 75~100 DEG C in plain compound, after then purifying by centrifugation and freeze-drying, obtains the phosphorous functional silicon
Change graphene oxide；The mass ratio of above-mentioned graphene oxide and phosphorous silicon element compound is 1: 10~50；
Above-mentioned first solvent is carbon tetrachloride or chloroform；
Above-mentioned second solvent is the mixed solvent of dehydrated alcohol, n,N-Dimethylformamide and deionized water composition；
Above-mentioned third solvent is toluene or acetone.
2. preparation method as described in claim 1, it is characterised in that: the time of the ultrasonic treatment is 30~60min.
3. preparation method as described in claim 1, it is characterised in that: the temperature of the hydrolysis is 78~100 DEG C.
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| CN109320773A (en) * | 2018-10-30 | 2019-02-12 | 中国民用航空飞行学院 | A kind of containing phosphorus silicon grafted graphene oxide fire retardant and preparation method thereof |
| CN110218327B (en) * | 2019-05-31 | 2021-03-16 | 福建师范大学 | Hyperbranched phosphorus-containing polysiloxane borane flame retardant and preparation method thereof |
| CN110510605B (en) * | 2019-08-05 | 2021-08-03 | 厦门大学 | Nitrogen-rich group functionalized graphene, and preparation method and application thereof |
| CN111849270B (en) * | 2020-07-29 | 2021-12-10 | 陕西科技大学 | Nitrogen, phosphorus and silicon synergistic coal flame-retardant dust suppressant and preparation method thereof |
| CN115010993A (en) * | 2022-07-14 | 2022-09-06 | 广东鼎立森新材料有限公司 | Preparation method and application of graphene oxide hybrid flame retardant |
| CN115477827B (en) * | 2022-10-18 | 2023-09-26 | 北京服装学院 | Preparation method and application of phosphorus-nitrogen-silicon composite intumescent flame retardant |
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| CN105001451A (en) * | 2015-06-12 | 2015-10-28 | 同济大学 | Graphene containing DOPO group and preparation method thereof |
| CN106752681B (en) * | 2016-11-23 | 2019-05-14 | 厦门大学 | A kind of Water-borne inflation type refractory coating and preparation method thereof based on modified graphene oxide |
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