CN108586807A - A kind of flame retarding function graphite alkene and its preparation and application - Google Patents
A kind of flame retarding function graphite alkene and its preparation and application Download PDFInfo
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- CN108586807A CN108586807A CN201810516709.5A CN201810516709A CN108586807A CN 108586807 A CN108586807 A CN 108586807A CN 201810516709 A CN201810516709 A CN 201810516709A CN 108586807 A CN108586807 A CN 108586807A
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Abstract
The invention discloses a kind of flame retarding function graphite alkene and its preparations and application, belong to field of fire-proof technology.The present invention makes flame retarding function graphite alkene be significantly improved the flame retardant property and thermal stability of polymeric matrix in surface of graphene oxide graft aminosilicones or 9,10 dihydro, 9 oxa-, 10 phospho hetero phenanthrene, 10 oxide；The present invention is also simultaneously in GO surface grafting long chain aminos siloxanes, aminoethylpiperazine and 9,10 dihydro, 9 oxa-, 10 phospho hetero phenanthrene, 10 oxide, flame retarding function graphite alkene is set to produce synergistic effect between each component while having both the above advantage, the flame retardant property for further enhancing flame retarding function graphite alkene is more suitable for the fire-retardant of polymeric matrix especially epoxy resin.
Description
Technical field
The invention belongs to field of fire-proof technology, more specifically to a kind of flame retarding function graphite alkene and its prepare and
Using.
Background technology
Epoxy resin (EP) be it is a kind of being widely used general thermosetting polymer, be mainly used in face coat, sealing
Material, composite material, insulating materials etc., have the advantages that toughness is strong, cure shrinkage is low, solvent resistant and chemical corrosivity it is good with
And outstanding electrical property, mechanical performance.It since EP is mainly made of carbon, hydrogen, oxygen element, easily burns, is giving people's lives band
Come while facility, also under cover huge fire safety evaluating hidden danger.Flame-retardant modified therefore, it is necessary to be carried out to EP, EP hinders at present
The shortcomings of firing agent that there are efficiency be low, thermal stability is poor and easy precipitation.
Invention content
1. to solve the problems, such as
It is inflammable and EP fire retardants have the shortcomings of efficiency is low, thermal stability is poor and easy precipitation for EP,
One of the objects of the present invention is to provide a kind of flame retarding function graphite alkene；The second object of the present invention is to provide the fire-retardant work(
The preparation method of energy graphite alkene；The third object of the present invention is to utilize nanometer composite technology, by functionalization graphene application
In EP nanocomposites.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of flame retarding function graphite alkene, structural formula are：
In formula, sheet carbon structure indicates graphene oxide (GO)；
A isB is-OH；
Or
A isB is
Or
A isB is
A kind of preparation method of foregoing flame retardant functionalization graphene, when A is When B is-OH, the flame retarding function graphite alkene is prepared by the following method：
Step 1, graphene oxide is dispersed in solvent, crane span structure intermediate is added, is stirred to react under the conditions of starvation,
Through being filtered, washed, being dried to obtain product one after the completion of reaction；The mass ratio of the graphene oxide and crane span structure intermediate is
(0.01~2):1,200~400mL solvents are added in every gram of graphene oxide, the crane span structure intermediate is long chain amino siloxanes
Or aminoethylpiperazine (AEP)；
Step 2, product one and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) are dispersed to solvent
In, triethylamine is added and carbon tetrachloride is reacted, after completion of the reaction through being filtered, washed, drying to get flame retarding function graphite
Alkene；The mass ratio of the product one, DOPO and triethylamine is (0.1~2):(1~30):(8~30) are added in every gram of product one
200~400mL solvents and 10~30mL carbon tetrachloride.
Further, the reaction condition in the step 1 is 80~95 DEG C of 6~12h of reaction, the reaction in the step 2
Condition be 0~5 DEG C reaction 12~for 24 hours.
Further, the solvent in the step 1 is selected from n,N-Dimethylformamide, water, acetone or tetrahydrofuran, described
Solvent in step 2 is dichloromethane or tetrahydrofuran.
A kind of preparation method of foregoing flame retardant functionalization graphene, when A isB isWhen, the flame retarding function graphite alkene is prepared by the following method：
Step 1, graphene oxide is dispersed in solvent, long chain amino siloxanes is added, is stirred under the conditions of starvation
Reaction, through being filtered, washed, being dried to obtain product two after the completion of reaction；The matter of the graphene oxide and long chain amino siloxanes
Amount is than being (0.02~2):1,200~400mL solvents are added in every gram of graphene oxide；
Step 2, product two is dispersed in solvent, AEP, dicyclohexylcarbodiimide (DCC) and 4- dimethylaminos is added
Pyridine (DMAP) is stirred to react under the conditions of starvation, through being filtered, washed, being dried to obtain product three after the completion of reaction；The production
Object two, AEP, DCC and DMAP mass ratio be (0.1~2):(1~5):(1~5):(0.5~2) is added in every gram of product two
200~400mL solvents；
Step 3, product three, DOPO are dispersed in solvent, triethylamine is added and carbon tetrachloride is reacted, reaction finishes
By being filtered, washed, dry to get flame retarding function graphite alkene；The mass ratio of the product three, DOPO and triethylamine is (0.1
~2):(1~30):(10~30), addition 200~400mL solvents and 10~30mL carbon tetrachloride in every gram of product three.
A kind of preparation method of foregoing flame retardant functionalization graphene, when A isB isWhen, the flame retarding function graphite alkene is prepared by the following method：
Step 1, graphene oxide is dispersed in solvent, AEP is added, is stirred to react, has reacted under the conditions of starvation
Cheng Houjing is filtered, washed, is dried to obtain product four；The mass ratio of the graphene oxide and AEP are (0.02~2):1, every gram
200~400mL solvents are added in graphene oxide；
Step 2, product four is dispersed in solvent, long chain amino siloxanes, DCC and DMAP, starvation condition is added
Under be stirred to react, through being filtered, washed, being dried to obtain product five after the completion of reaction；The product four, long chain amino siloxanes, DCC
Mass ratio with DMAP is (0.1~2):(1~5):(1~5):(0.5~2), 200~400mL of addition is molten in every gram of product four
Agent；
Step 3, product five, DOPO are dispersed in solvent, triethylamine is added and carbon tetrachloride is reacted, reaction finishes
By being filtered, washed, dry to get flame retarding function graphite alkene；The mass ratio of the product five, DOPO and triethylamine is (0.1
~2):(1~30):(10~30), addition 200~400mL solvents and 10~30mL carbon tetrachloride in every gram of product five.
Further, the reaction condition in the step 1 is 80~95 DEG C of 6~12h of reaction, the reaction in the step 2
Condition is that 12~36h is reacted at 70~90 DEG C, the reaction condition that carbon tetrachloride is added in the step 3 be 0~5 DEG C of reaction 12~
24h。
Further, the solvent in the step 1 is selected from n,N-Dimethylformamide, water, acetone or tetrahydrofuran, institute
It states the solvent in step 2 and is selected from n,N-Dimethylformamide, acetone or tetrahydrofuran, the solvent in the step 3 is dichloromethane
Alkane or tetrahydrofuran.
The invention further relates to a kind of application of foregoing flame retardant functionalization graphene in EP.
As one kind of phosphorus flame retardant, since there are cyclohexyl biphenyl, phenanthrene ring, O=P-O keys in the structural formula of DOPO, so
It stablizes than general organic phosphorus compound, and flame retardant effect is more preferable.DOPO and its derivative can play gas phase in combustion
Fire-retardant effect has good burning self-extinguishment, flame retardant effect excellent.
The property of graphene shows good application in photoelectric material, energy storage material, electronic device etc.
Foreground, and graphene is equally pleasurable in the application prospect of fire-retardant aspect, the unique two-dimensional structure of graphene so that graphene
There is good physical barrier effect in polymer composites, fire retardation can be played, on the one hand can reduce matrix
The heat release rate of burning；On the other hand, the presence of graphene filler can not only significantly improve composite material tensile strength,
The mechanical properties such as bending strength can also improve the thermal stability and thermal conductivity of composite material.
3. advantageous effect
Compared with the prior art, beneficial effects of the present invention are:The present invention in GO surface grafting long chain amino siloxanes or
DOPO makes flame retarding function graphite alkene be significantly improved the flame retardant property and thermal stability of polymeric matrix.
There are very strong interactions between graphene sheet layer, are easy to occur in using and preparing composite material
Agglomeration.In GO surface grafting AEP and DOPO the dispersibility of graphene in a polymer matrix can be improved, effectively in the present invention
Improve the reunion behavior of graphene, while flame retardant property also can be improved.
The present invention also simultaneously in GO surface graftings amino silicone, AEP and DOPO, makes flame retarding function graphite alkene have both
Synergistic effect is produced while the above advantage between each component, the anti-flammability of flame retarding function graphite alkene can be further enhanced
Can, it is more suitable for the fire-retardant of polymeric matrix especially EP.
Specific implementation mode
The present invention is further described below with reference to specific embodiment.
GO employed in following embodiment and comparative example is prepared for Hummers methods, the specific steps are：By 4g graphite powders
The 100mL concentrated sulfuric acids are added to, are placed in ice-water bath, 12g potassium permanganate is added while stirring, it is small to continue stirring 2 in ice-water bath
Shi Hou is stirred at room temperature 1 hour, is slowly added to 100mL deionized waters, continues stirring after twenty minutes, and 650mL deionizations are added
Water and 50mL hydrogen peroxide.With 10% salt acid elution after suction filtration, graphite oxide is obtained after washing multipass to neutrality；By what is prepared
Graphite oxide is scattered in DMF, and the suspension of GO can be obtained after ultrasonic 1.5h, is filtered after drying up to GO powders.
The EP trades mark employed in following embodiment and comparative example are to purchase from Xingchen Synthetic Matrials Co., Ltd., Nantong
0164R.
Fire-retardant EP made from following embodiment test as follows：
Limit oxygen index (LOI) is tested:By ASTMD2863 standards, sample size is 100 × 6.7 × 3mm3Experiment sample
Item, and tested using HC-2 type LOI instrument (Jiangning Instrumental Analysis company).
UL-94 vertical burn tests:According to ASTM D3801-1996 standards, prepare batten size be 127 × 12.7 ×
3mm3, and tested using CFZ-2 type horizontal verticals burning analyzer (Jiangning analytical instrument factory).
Embodiment 1
1g GO are dispersed in 300mL DMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 3g long chain aminos are added
Siloxanes, under nitrogen protection, return stirring reacts 10h at 85 DEG C.It waits for after reaction, filtering after product is cooled to room temperature,
Filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol successively, 80 DEG C of drying 12h are produced in vacuum drying chamber
Object one.
1g products one, 17.5g DOPO are dispersed in 300mL dichloromethane, tri- mouthfuls of burnings of 500mL are poured into after ultrasonic 0.5h
Bottle is added 20.2g TEA, three-necked flask is placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by 19.5mL
Carbon tetrachloride is added dropwise into reaction bulb, and reaction temperature is no more than 5 DEG C, is stirred to react for 24 hours, entire reaction process is under nitrogen protection
It carries out, after reaction dries product filtration washing, the structural formula for obtaining final product is：
Suitable final product is added in EP and is stirred continuously 1h, with EP and 4,4 '-diamino hexichol of epoxy hardener
Methane (DDM) mass ratio is 5:1, DDM is uniformly mixed with mixture, mold is placed in and is put into baking oven, cure at 100 DEG C
2h is warming up to 150 DEG C of solidification 2h.Flame retardant property test is carried out to obtained nanocomposite, the results are shown in Table 1.Work as additive amount
When being 6%, limit oxygen index (LOI) is that 29.2%, UL-94 vertical burn test flame retardant ratings reach V-0 grades.
The performance test of the fire-retardant EP of the different adding proportions of 1 embodiment of table 1
Embodiment 2
1g GO are dispersed in 300mL DMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 3g long-chain amidos are added
Siloxanes, under nitrogen protection, return stirring reacts 10h at 85 DEG C.It waits for after reaction, filtering after product is cooled to room temperature,
Filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol respectively, 80 DEG C of drying 12h are produced in vacuum drying chamber
Object one.
1g products one, 10g DOPO are dispersed in 300mL dichloromethane, 500mL three-necked flasks are poured into after ultrasonic 0.5h,
10g TEA are added, three-necked flask are placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by 20mL carbon tetrachloride
It is added dropwise into reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react for 24 hours, entire reaction process carries out under nitrogen protection, instead
Product filtration washing is dried after answering, obtains final product.
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test.When additive amount is 6%, the LOI of composite material is that 29.5%, UL-94 vertically fires
It burns test flame retardant rating and reaches V-0 grades.
Embodiment 3
1g GO are dispersed in 200mL water, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 100g long-chain amidos are added
Siloxanes, under nitrogen protection, return stirring reacts 12h at 80 DEG C.It waits for after reaction, filtering after product is cooled to room temperature,
Filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol respectively, 80 DEG C of drying 12h are produced in vacuum drying chamber
Object one.
2g products one, 30g DOPO are dispersed in 400mL tetrahydrofurans, 500mL three-necked flasks are poured into after ultrasonic 0.5h,
30g TEA are added, three-necked flask are placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by 10mL carbon tetrachloride
It is added dropwise into reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react 12h, entire reaction process carries out under nitrogen protection, instead
Product filtration washing is dried after answering, obtains final product.
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test.When additive amount is 6%, the LOI of composite material is that 29.1%, UL-94 vertically fires
It burns test flame retardant rating and reaches V-0 grades.
Embodiment 4
1g GO are dispersed in 400mL tetrahydrofurans, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 0.5g long is added
Chain amido siloxanes, under nitrogen protection, return stirring reacts 6h at 95 DEG C.It waits for after reaction, after product is cooled to room temperature
Filter cake, is scattered in supersound washing 0.5h in deionized water and ethyl alcohol by filtering respectively, and 80 DEG C of drying 12h are obtained in vacuum drying chamber
To product one.
0.1g products one, 1g DOPO are dispersed in 200mL dichloromethane, tri- mouthfuls of burnings of 500mL are poured into after ultrasonic 0.5h
Bottle is added 10g TEA, three-necked flask is placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by 30mL tetrachloros
Change carbon to be added dropwise into reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react 20h, entire reaction process under nitrogen protection into
Row, product filtration washing is dried, obtain final product after reaction.
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test.When additive amount is 6%, the LOI of composite material is that 29.6%, UL-94 vertically fires
It burns test flame retardant rating and reaches V-0 grades.
Embodiment 5
1g GO are dispersed in 300mL DMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 6g AEP, nitrogen is added
Under gas shielded, return stirring reacts 6h at 95 DEG C.It waits for being cooled to room temperature filtering after reaction, filter cake is scattered in respectively
Supersound washing 0.5h in ionized water and ethyl alcohol, 80 DEG C of drying 12h obtain product one in vacuum drying chamber.
1g products one, 17.5g DOPO are dispersed in 300mL THF, 500mL three-necked flasks are poured into after ultrasonic 0.5h, are added
Enter 8.21g TEA, three-necked flask is placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by tetra- chlorinations of 19.5mL
Carbon is added dropwise into reaction bulb, and reaction temperature is no more than 5 DEG C, is stirred to react 12h, and entire reaction process carries out under nitrogen protection,
Filtration washing is dried in vacuo to obtain final product, and concrete structure formula is：
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test, the results are shown in Table 2.When additive amount is only 2%, LOI 29.8%, UL-94 hang down
Straight combustion testing flame retardant rating reaches V-0 grades.
The performance test of the fire-retardant EP of the different adding proportions of 2 embodiment of table 5
Embodiment 6
1g GO are dispersed in 300mL DMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 6g AEP, nitrogen is added
Under gas shielded, return stirring reacts 6h at 95 DEG C.It waits for being cooled to room temperature filtering after reaction, filter cake is scattered in respectively
Supersound washing 0.5h in ionized water and ethyl alcohol, 80 DEG C of drying 12h obtain product one in vacuum drying chamber.
1g products one, 10g DOPO are dispersed in 300mL THF, 500mL three-necked flasks are poured into after ultrasonic 0.5h, is added
10g TEA, three-necked flask is placed in cryogenic thermostat stirring reactive bath, and when temperature is down to 0 DEG C, 20mL carbon tetrachloride is added dropwise
Into in reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react 12h, and entire reaction process carries out under nitrogen protection, crosses diafiltration
It washs vacuum drying and obtains final product.
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in grinding tool and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test.When additive amount is only 2%, LOI 29.8%, UL-94 vertical burn tests
Flame retardant rating reaches V-0 grades.
Embodiment 7
1g GO are dispersed in 300mL DMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 3g long-chain amidos are added
Siloxanes, under nitrogen protection, return stirring reacts 10h at 85 DEG C.It waits for after reaction, filtering after product is cooled to room temperature,
Filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol respectively, 80 DEG C of drying 12h are produced in vacuum drying chamber
Object two.
1g products two are dispersed in 300mLDMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 3g AEP are added,
2gDCC (DCC), 1g DMAP (DMAP), under nitrogen protection, return stirring reacts for 24 hours at 80 DEG C.It waits for cooling down after reaction
It is filtered to room temperature, filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol respectively, 80 DEG C of bakings in vacuum drying chamber
Dry 12h obtains product three.
1g products three, 20g DOPO are dispersed in 300mL THF, 500mL three-necked flasks are poured into after ultrasonic 0.5h, is added
20.2g TEA, three-necked flask is placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by 19.5mL carbon tetrachloride
It is added dropwise into reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react 12h, entire reaction process carries out under nitrogen protection.Instead
Filtration washing after answering, 80 DEG C of drying 12h obtain final product in vacuum drying chamber, and concrete structure formula is：
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test, the results are shown in Table 3.When additive amount is 4%, LOI 29.9%, UL-94 is vertical
Combustion testing flame retardant rating reaches V-0 grades.
The performance test of the fire-retardant EP of the different adding proportions of 3 embodiment of table 7
Embodiment 8
1g GO are dispersed in 300mL DMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 3g long-chain amidos are added
Siloxanes, under nitrogen protection, return stirring reacts 10h at 85 DEG C.It waits for after reaction, filtering after product is cooled to room temperature,
Filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol respectively, 80 DEG C of drying 12h are produced in vacuum drying chamber
Object two.
1g products two are dispersed in 300mLDMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 5g AEP are added,
3g DCC and 2g DMAP, under nitrogen protection, return stirring reacts for 24 hours at 80 DEG C.It waits for being cooled to room temperature after reaction
Filter cake, is scattered in supersound washing 0.5h in deionized water and ethyl alcohol by filter respectively, and 80 DEG C of drying 12h are obtained in vacuum drying chamber
Product three.
1g products three, 20g DOPO are dispersed in 300mL THF, 500mL three-necked flasks are poured into after ultrasonic 0.5h, is added
20.2g TEA, three-necked flask is placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by 19.5mL carbon tetrachloride
It is added dropwise into reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react 12h, entire reaction process carries out under nitrogen protection.Instead
Filtration washing after answering, 80 DEG C of drying 12h obtain final product in vacuum drying chamber.
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test.When additive amount is 4%, LOI 30.3%, the resistance of UL-94 vertical burn tests
It fires grade and reaches V-0 grades.
Embodiment 9
1g GO are dispersed in 200mL water, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 50g long chain aminos are added
Siloxanes, under nitrogen protection, return stirring reacts 12h at 80 DEG C.It waits for after reaction, filtering after product is cooled to room temperature,
Filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol respectively, 80 DEG C of drying 12h are produced in vacuum drying chamber
Object two.
0.1g products two are dispersed in 400mL tetrahydrofurans, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, are added
1g AEP, 5g DCC, 2g DMAP, under nitrogen protection, return stirring reacts 12h at 90 DEG C.It waits for being cooled to after reaction
Room temperature filters, and filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol respectively, 80 DEG C of drying in vacuum drying chamber
12h obtains product three.
2g products three, 30g DOPO are dispersed in 400mL dichloromethane, 500mL three-necked flasks are poured into after ultrasonic 0.5h,
10g TEA are added, three-necked flask are placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by 30mL carbon tetrachloride
It is added dropwise into reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react for 24 hours, entire reaction process carries out under nitrogen protection.Instead
Filtration washing after answering, 80 DEG C of drying 12h obtain final product in vacuum drying chamber.
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test.When additive amount is 4%, LOI 30.1%, the resistance of UL-94 vertical burn tests
It fires grade and reaches V-0 grades.
Embodiment 10
1g GO are dispersed in 400mL tetrahydrofurans, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 0.5g long is added
Chain amino silicone, under nitrogen protection, return stirring reacts 6h at 95 DEG C.It waits for after reaction, after product is cooled to room temperature
Filter cake, is scattered in supersound washing 0.5h in deionized water and ethyl alcohol by filtering respectively, and 80 DEG C of drying 12h are obtained in vacuum drying chamber
To product two.
2g products two are dispersed in 200mL acetone, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 5g AEP are added,
1g DCC, 0.5g DMAP, under nitrogen protection, return stirring reacts 36h at 70 DEG C.It waits for being cooled to room temperature after reaction
Filter cake, is scattered in supersound washing 0.5h in deionized water and ethyl alcohol by filter respectively, and 80 DEG C of drying 12h are obtained in vacuum drying chamber
Product three.
0.1g products three, 1g DOPO are dispersed in 200mL THF, 500mL three-necked flasks are poured into after ultrasonic 0.5h, are added
Enter 30g TEA, three-necked flask is placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, 10mL carbon tetrachloride is dripped
It adds in reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react 20h, entire reaction process carries out under nitrogen protection.Reaction
After filtration washing, in vacuum drying chamber 80 DEG C drying 12h obtain final product.
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test.When additive amount is 4%, LOI 30.5%, the resistance of UL-94 vertical burn tests
It fires grade and reaches V-0 grades.
Embodiment 11
1g GO are dispersed in 300mL DMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 6g AEP, nitrogen is added
Under gas shielded, return stirring reacts 6h at 95 DEG C.It waits for being cooled to room temperature filtering after reaction, filter cake is scattered in respectively
Supersound washing 0.5h in ionized water and ethyl alcohol, 80 DEG C of drying 12h obtain product four in vacuum drying chamber.
1g products four are dispersed in 300mL DMF, 500mL three-necked flasks are poured into after ultrasonic disperse 1h, 3g long-chains are added
Amino silicone, 2g DCC, 1g DMAP, under nitrogen protection, return stirring reacts for 24 hours at 80 DEG C.It waits for cold after reaction
But it is filtered to room temperature, filter cake is scattered in supersound washing 0.5h in deionized water and ethyl alcohol respectively, 80 DEG C in vacuum drying chamber
Drying 12h obtains product five.
1g products five, 20g DOPO are dispersed in 300mL THF, 500mL three-necked flasks are poured into after ultrasonic 0.5h, is added
20.2g TEA, three-necked flask is placed in cryogenic thermostat stirring reactive bath, when temperature is down to 0 DEG C, by 19.5mL carbon tetrachloride
It is added dropwise into reaction bulb, reaction temperature is no more than 5 DEG C, is stirred to react 12h, entire reaction process carries out under nitrogen protection.Instead
Filtration washing after answering, 80 DEG C of drying 12h obtain final product in vacuum drying chamber, and concrete structure formula is：
Suitable final product is added in EP and is stirred continuously 1h, with epoxy and DDM mass ratioes for 5:1, by DDM and mix
It closes object uniformly to mix, is placed in mold and is put into baking oven, cure 2h at 100 DEG C, be warming up to 150 DEG C of solidification 2h.To what is obtained
Nanocomposite carries out flame retardant property test.When additive amount is 4%, LOI 30%, UL-94 vertical burn tests are fire-retardant
Grade reaches V-0 grades.
Claims (9)
1. a kind of flame retarding function graphite alkene, which is characterized in that its structural formula is：
In formula, sheet carbon structure indicates graphene oxide；
A isB is-OH；
Or
A isB is
Or
A isB is
2. a kind of preparation method of flame retarding function graphite alkene as described in claim 1, which is characterized in that when A isWhen B is-OH, the flame retarding function
Graphene is prepared by the following method：
Step 1, graphene oxide is dispersed in solvent, crane span structure intermediate is added, is stirred to react under the conditions of starvation, reacts
After the completion through being filtered, washed, being dried to obtain product one；The mass ratio of the graphene oxide and crane span structure intermediate be (0.01~
2):1,200~400mL solvents are added in every gram of graphene oxide, the crane span structure intermediate is long chain amino siloxanes or amino
Ethyl piperazidine；
Step 2, product one and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are dispersed in solvent, three second is added
Amine and carbon tetrachloride are reacted, after completion of the reaction through being filtered, washed, drying to get flame retarding function graphite alkene；The product
One, the mass ratio of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies and triethylamine is (0.1~2):(1~30):(8
~30) 200~400mL solvents and 10~30mL carbon tetrachloride, are added in every gram of product one.
3. the preparation method of flame retarding function graphite alkene according to claim 2, which is characterized in that in the step 1
Reaction condition is 80~95 DEG C of 6~12h of reaction, and the reaction condition in the step 2 is 0~5 DEG C of reaction 12~for 24 hours.
4. the preparation method of flame retarding function graphite alkene according to claim 2, which is characterized in that in the step 1
Solvent is selected from n,N-Dimethylformamide, water, acetone or tetrahydrofuran, and the solvent in the step 2 is dichloromethane or tetrahydrochysene
Furans.
5. a kind of preparation method of flame retarding function graphite alkene as described in claim 1, which is characterized in that when A isB isWhen, the flame retarding function graphite alkene is logical
Cross following methods preparation:
Step 1, graphene oxide is dispersed in solvent, long chain amino siloxanes is added, is stirred to react under the conditions of starvation,
Through being filtered, washed, being dried to obtain product two after the completion of reaction；The mass ratio of the graphene oxide and long chain amino siloxanes is
(0.02~2):1,200~400mL solvents are added in every gram of graphene oxide；
Step 2, product two is dispersed in solvent, aminoethylpiperazine, dicyclohexylcarbodiimide and 4- dimethylaminos is added
Pyridine is stirred to react under the conditions of starvation, through being filtered, washed, being dried to obtain product three after the completion of reaction；The product two,
The mass ratio of aminoethylpiperazine, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is (0.1~2):(1~5):(1~
5):(0.5~2) adds 200~400mL solvents in every gram of product two；
Step 3, product three, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are dispersed in solvent, three second is added
Amine and carbon tetrachloride are reacted, after completion of the reaction through being filtered, washed, drying to get flame retarding function graphite alkene；The product
Three, the mass ratio of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies and triethylamine is (0.1~2):(1~30):(10
~30) 200~400mL solvents and 10~30mL carbon tetrachloride, are added in every gram of product three.
6. a kind of preparation method of flame retarding function graphite alkene as described in claim 1, which is characterized in that when A isB isWhen, the flame retarding function graphite alkene is logical
Cross following methods preparation：
Step 1, graphene oxide is dispersed in solvent, aminoethylpiperazine is added, is stirred to react under the conditions of starvation, instead
It should be after the completion through being filtered, washed, being dried to obtain product four；The graphene oxide and the mass ratio of aminoethylpiperazine are
(0.02~2):1,200~400mL solvents are added in every gram of graphene oxide；
Step 2, product four is dispersed in solvent, long chain amino siloxanes, dicyclohexylcarbodiimide and 4- diformazan ammonia is added
Yl pyridines are stirred to react under the conditions of starvation, through being filtered, washed, being dried to obtain product five after the completion of reaction；The product
Four, the mass ratio of long chain amino siloxanes, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is (0.1~2):(1~5):
(1~5):(0.5~2) adds 200~400mL solvents in every gram of product four；
Step 3, product five, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are dispersed in solvent, three second is added
Amine and carbon tetrachloride are reacted, after completion of the reaction through being filtered, washed, drying to get flame retarding function graphite alkene；The product
Five, the mass ratio of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies and triethylamine is (0.1~2):(1~30):(10
~30) 200~400mL solvents and 10~30mL carbon tetrachloride, are added in every gram of product five.
7. the preparation method of flame retarding function graphite alkene according to claim 5 or 6, which is characterized in that in the step 1
Reaction condition be 80~95 DEG C of 6~12h of reaction, the reaction condition in the step 2 is that 12~36h is reacted at 70~90 DEG C,
In the step 3 be added carbon tetrachloride reaction condition be 0~5 DEG C reaction 12~for 24 hours.
8. the preparation method of flame retarding function graphite alkene according to claim 7, which is characterized in that in the step 1
Solvent is selected from n,N-Dimethylformamide, water, acetone or tetrahydrofuran, and the solvent in the step 2 is selected from N, N- dimethyl methyls
Amide, acetone or tetrahydrofuran, the solvent in the step 3 are dichloromethane or tetrahydrofuran.
9. a kind of application of flame retarding function graphite alkene as described in claim 1 in the epoxy.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229191A (en) * | 2019-06-21 | 2019-09-13 | 福建师范大学 | A kind of DOPO base reactive flame retardant and preparation method thereof containing piperazine structure |
| CN110256814A (en) * | 2019-06-21 | 2019-09-20 | 福建师范大学 | A kind of preparation method of the derivative modified fire retarding epoxide resin of DOPO containing piperazine structure |
| KR20200144900A (en) * | 2019-06-19 | 2020-12-30 | 한국과학기술연구원 | Functionalized graphene oxide and preparing method thereof |
| CN115490996A (en) * | 2022-09-28 | 2022-12-20 | 山东博克塞斯新材料科技有限公司 | Epoxy resin composite material and processing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104024266A (en) * | 2011-08-08 | 2014-09-03 | 联邦材料测试与开发研究所 | Novel phosphonamidates-synthesis and flame retardant applications |
| CN104804477A (en) * | 2015-03-26 | 2015-07-29 | 苏州安鸿泰新材料有限公司 | Preparation method and application of modified graphene nano filling material |
| CN106883450A (en) * | 2017-02-20 | 2017-06-23 | 无锡市惠山区川大石墨烯应用研究中心 | A kind of rich phosphatization Graphene fire retardant and preparation method thereof |
-
2018
- 2018-05-25 CN CN201810516709.5A patent/CN108586807B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104024266A (en) * | 2011-08-08 | 2014-09-03 | 联邦材料测试与开发研究所 | Novel phosphonamidates-synthesis and flame retardant applications |
| CN104804477A (en) * | 2015-03-26 | 2015-07-29 | 苏州安鸿泰新材料有限公司 | Preparation method and application of modified graphene nano filling material |
| CN106883450A (en) * | 2017-02-20 | 2017-06-23 | 无锡市惠山区川大石墨烯应用研究中心 | A kind of rich phosphatization Graphene fire retardant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| NETHRAVATHI C 等: "The production of smectite clay/graphene composites through delamination and co-stacking", 《CARBON》 * |
| Y. MATSUO 等: "Synthesis of polyaniline-intercalated layered materials via exchange reaction", 《JOURNAL OF MATETIALS CHEMISTRY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200144900A (en) * | 2019-06-19 | 2020-12-30 | 한국과학기술연구원 | Functionalized graphene oxide and preparing method thereof |
| KR102225469B1 (en) * | 2019-06-19 | 2021-03-10 | 한국과학기술연구원 | Functionalized graphene oxide and preparing method thereof |
| CN110229191A (en) * | 2019-06-21 | 2019-09-13 | 福建师范大学 | A kind of DOPO base reactive flame retardant and preparation method thereof containing piperazine structure |
| CN110256814A (en) * | 2019-06-21 | 2019-09-20 | 福建师范大学 | A kind of preparation method of the derivative modified fire retarding epoxide resin of DOPO containing piperazine structure |
| CN110256814B (en) * | 2019-06-21 | 2022-02-22 | 福建师范大学 | Preparation method of piperazine structure-containing DOPO derivative modified flame-retardant epoxy resin |
| CN115490996A (en) * | 2022-09-28 | 2022-12-20 | 山东博克塞斯新材料科技有限公司 | Epoxy resin composite material and processing method thereof |
| CN115490996B (en) * | 2022-09-28 | 2023-06-27 | 山东博克塞斯新材料科技有限公司 | Epoxy resin composite material and processing method thereof |
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