CN105001451A - Graphene containing DOPO group and preparation method thereof - Google Patents
Graphene containing DOPO group and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of materials, and particularly relates to graphene containing a phosphorus based flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) group and a preparation method thereof. The preparation method includes the specific steps that first, graphene and DOPO are grafted to a specific chemical group through a chemical reaction, so that the DOPO with an epoxy group and the graphene with amino are obtained; second, the DOPO with the epoxy group is made to react with the graphene with the amino, so that the graphene with the DOPO group is obtained. The graphene with the DOPO group can improve the flame retardant properties of a high polymer and a composite material thereof, and meanwhile the mechanical properties of the material can be improved simultaneously or be kept to the greatest extent. The preparation method of the graphene containing the DOPO group is mild in technological condition, simple and easy to implement, and suitable for batch production.
Description
Technical field
The invention belongs to field of material technology, be specifically related to a kind of containing phosphorus flame retardant 9, Graphene of assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy and preparation method thereof, it may be used for the flame retardant properties and the mechanical property that improve superpolymer and matrix material thereof.
Background technology
Graphene (Graphene) is a kind of novel material of the individual layer sheet structure be made up of carbon atom.Being a kind ofly form with sp2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, is the two-dimensional material only having a carbon atom thickness.From Andre Geim in 2004 and Konstantin Novoselov successfully since Graphene is isolated in laboratory from graphite, Graphene is just because of the structure of its uniqueness, and good electrical property and mechanical property become the focus of Recent study.Meanwhile, owing to can form fine and close carbon-coating when Graphene burns on surface, so can become flame-retardant additive, part research has proved its flame retardant effect.Although add the mechanical property that Graphene can improve material in superpolymer and matrix material thereof, reduce the heat release rate of material simultaneously, but the degree added material combustion test feature improves of Graphene needs to be strengthened further, to meet the widespread use of matrix material in engineering.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a kind of reactive phosphorus flame retardant intermediate, and it has excellent flame retardant resistance, smokelessly nontoxic, because P mono-C key exists, chemical stability is good, water-fast, can permanent fire retardant and not moving.DOPO can be used for the polyester flame-retardants such as PET, PBT, PBN, PEN, the chemical modification of the macromolecular material such as ethoxyline resin antiflaming and polyvinyl alcohol.External being also widely used in plastics for electronics, brass presses layer, circuit card, photochromics and luminescent material fire-retardant.DOPO has hexa-atomic phosphorus heterocycle structure, and P has lone-pair electron, easily nucleophilic addition occurs.Although fire retardant DOPO adds in superpolymer can improve its flame retardant properties, the mechanical property of superpolymer also can be made to a certain extent to be deteriorated simultaneously.
Guobo Huang etc. find the nano composite material polymer solution blend based on polyvinyl alcohol and Graphene, evaluate its flame retardant properties with taper calorimetric test.Prove graphene nanometer sheet has the effect significantly reducing heat release rate peak value and the effect extending the some retardant composite material time, fire resistance is had a great impact.The people such as Chung Yuan find that the DOPO-PN that DOPO and 4-hydroxy benzaldehyde is synthesized by addition reaction has certain influence to the fire-retardant performance of matrix material, prove that DOPO-PN can make matrix material be tested by UL94V-0, can make the limiting oxygen index(LOI) of matrix material have larger lifting by experiment.Add described in patent ZL 201310008589.5, first modification is carried out to Graphene with the silane containing isocyano, then introduce DOPO structure again by sol-gel method, prepared the composite structure containing DOPO and leafing Graphene, the flame retardant properties of polymkeric substance can be improved.
In order to obtain the fire retardant material improving Flame Retardancy energy and mechanical property simultaneously, this patent provides a kind of preparation method of the Graphene containing DOPO group, by being grafted on Graphene by DOPO, can play the advantage of DOPO and Graphene simultaneously, maximize favourable factors and minimize unfavourable ones, formed complementary.This method has the simple feature of technique, and the fire retardant efficient stable obtained, has important actual application value.
Summary of the invention
The object of this invention is to provide a kind of Graphene containing DOPO group and preparation method thereof, this Graphene may be used in superpolymer and matrix material thereof, in the fire-retardant performance of raising matrix material simultaneously, improves or keep as far as possible the mechanical property of material.
For achieving the above object, solution of the present invention is: first respectively by Graphene and DOPO by chemical reaction with specified chemical group, obtain DOPO and the Graphene of modification.Again modified DOPO and Graphene are reacted, obtain the Graphene with DOPO group.
A kind of Graphene containing DOPO group that the present invention proposes, its following structural features:
Wherein: R is phenyl or methylene radical, n >=2.
In the present invention, described phenyl is
or
or
in one, methylene radical is-CH
2-or
, X>=2.
The preparation method of the Graphene containing DOPO group that the present invention proposes, concrete steps are:
(1) graphite oxide is dissolved in solvent, utilize ultrasonic disperse, add diamines and Dicyclohexylcarbodiimide (DCC), wherein graphite oxide and diamines weight ratio are 1:150, the weight ratio of diamines and Dicyclohexylcarbodiimide (DCC) is 1:100, stirring and refluxing 8 ~ 24h in the oil bath of 65 ~ 85 DEG C.After reaction terminates, filter, repetitive scrubbing.
(2) under nitrogen protection in four-hole boiling flask, add DOPO and solvent, heated and stirred, to 70 ~ 85 DEG C, after DOPO dissolves completely, adds para benzoquinone in 1.5h, and in DOPO and benzoquinones, weight ratio is 1:150, stirring reaction 2 ~ 4h at 90 DEG C.Gained throw out is cooled to room temperature to filter, washing for several times, obtains white powder after drying, then uses solvent recrystallization, can obtain white solid after drying.
(3), in the four-hole boiling flask white solid obtained in step (2) and epoxy chloropropane added according to weight ratio 1:150, proper catalyst is added, at 65 ~ 75 DEG C of reaction 18 ~ 24h.By products therefrom washing for several times, the DOPO with epoxy group(ing) is obtained after drying.
(4) dissolved by the epoxide group DOPO that step (3) obtains, the amination Graphene obtained with step (1) is according to weight ratio 1:150 heated and stirred 12h in 70 ~ 85 DEG C of oil baths.The product solvent repetitive scrubbing several obtained, dry 12h.Obtain the Graphene with DOPO group.
In the present invention, described Graphene comprises individual layer and multi-layer graphene.
In the present invention, the diamine structures formula described in step (3) is as follows:
Wherein R for for phenyl (
or
or
in one) or methylene radical (-CH
2-) or
(X>=2), n>=2.
In the present invention, described in step (2), (3) and (4), solvent comprises one or more in methyl alcohol, ethanol, propyl alcohol, dimethyl sulfoxide (DMSO), benzene,toluene,xylene, methylene dichloride, chloroform, acetone, butanone, tetrahydrofuran (THF) or dimethyl formamide etc.
In the present invention, the weight ratio using the amount of solvent should meet Graphene and solvent or DOPO and solvent described in step (1), (2), (3) and (4) is 1 ~ 150.
In the present invention, described in step (3), catalyzer is sodium methylate, one or more in potassium hydroxide or sodium hydroxide etc.
Beneficial effect of the present invention is:
(1) DOPO group is grafted on Graphene, can obtains a kind of efficient, stable fire retardant.
(2) this Graphene with DOPO group can be used for the fire-retardant of superpolymer and matrix material thereof, raising Flame Retardancy can while, keep as far as possible or improve the mechanical property of material.
(3) preparation method is simple effectively, processing condition are gentle, is applicable to batch production.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the Graphene of the grafting DOPO group of embodiment 1.Wherein 1191cm
-1neighbouring peak represents the vibration peak of P=O; 1075cm
-1neighbouring peak represents the vibration peak of P-O-C; 1410cm
-1the vibration peak of peak representation hydroxy.These all illustrate, Graphene grafted epoxy DOPO is successfully prepared.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
(1) 0.5g graphite oxide is dissolved in ultrasonic disperse in DMF solution, adds 50ml quadrol, the Dicyclohexylcarbodiimide (DCC) of 3g, stirring and refluxing 8h in the oil bath of 65 DEG C.Reaction terminate after, filter, then with DMF solution repetitive scrubbing until excessive ethylenediamine solution all washes away.
(2) under nitrogen protection in four-hole boiling flask, add 12gDOPO and 300mL toluene, heated and stirred, to 70 DEG C, after DOPO is dissolved in toluene completely, adds 5g benzoquinones in 1.5h, afterwards stirring reaction 2h at 90 DEG C.Gained throw out is cooled to room temperature to filter, toluene wash for several times, obtains white powder after drying, then heavily ties product with ethanol, can obtain white solid after drying.
In the four-hole boiling flask that (3) 32.4 g white solids and 100mL epoxy chloropropane add, add 15g sodium methylate as catalyzer, at 65 DEG C of reaction 18h.By products therefrom methanol wash several, after drying, obtain the DOPO with epoxy group(ing).
(4) the epoxide group DOPO that step (3) obtains is dissolved, the amination Graphene obtained with step (1) heated and stirred 12h in 70 DEG C of oil baths.The product dehydrated alcohol repetitive scrubbing several obtained, dry 12h.Obtain the Graphene with DOPO group.
Embodiment 2
(1) 0.4g graphite oxide is dissolved in ultrasonic disperse in toluene solution, adds 50ml triethylene tetramine, the Dicyclohexylcarbodiimide (DCC) of 3.5g, stirring and refluxing 8.5h in the oil bath of 67 DEG C.Reaction terminate after, filter, then with toluene solution repetitive scrubbing until excessive triethylene tetramine solution all washes away.
(2) under nitrogen protection in four-hole boiling flask, add 12gDOPO and 300mL chlorobenzene, heated and stirred, to 72 DEG C, after DOPO is dissolved in chlorobenzene completely, adds 5g benzoquinones in 1.5h, afterwards stirring reaction 2.5h at 90 DEG C.Gained throw out is cooled to room temperature to filter, chlorobenzene washing for several times, obtains white powder after drying, then heavily ties product with ethanol, can obtain white solid after drying.
(3) in the four-hole boiling flask that 35g white solid and 120mL epoxy chloropropane add, 15.5g sodium methylate is added as catalyzer, at 68 DEG C of reaction 18.5h.By products therefrom methanol wash several, after drying, obtain the DOPO with epoxy group(ing).
(4) the epoxide group DOPO that step (3) obtains is dissolved, the amination Graphene obtained with step (1) heated and stirred 12h in 72 DEG C of oil baths.The product dehydrated alcohol repetitive scrubbing several obtained, dry 12h.Obtain the Graphene with DOPO group.
Embodiment 3
(1) 0.6g graphite oxide is dissolved in ultrasonic disperse in THF solution, adds 60ml Ursol D, the Dicyclohexylcarbodiimide (DCC) of 3g, stirring and refluxing 12h in the oil bath of 70 DEG C.Reaction terminate after, filter, then with THF solution repetitive scrubbing until excessive Ursol D solution all washes away.
(2) under nitrogen protection in four-hole boiling flask, add 12gDOPO and 300mL toluene, heated and stirred, to 75 DEG C, after DOPO is dissolved in toluene completely, adds 5g benzoquinones in 1.5h, afterwards stirring reaction 2.5h at 90 DEG C.Gained throw out is cooled to room temperature to filter, toluene wash for several times, obtains white powder after drying, then heavily ties product with ethanol, can obtain white solid after drying.
In the four-hole boiling flask that (3) 32.4 g white solids and 150mL epoxy chloropropane add, add KOH(0.5mol/L) as catalyzer, at 67 DEG C of reaction 19h.By products therefrom methanol wash several, after drying, obtain the DOPO with epoxy group(ing).
(4) the epoxide group DOPO that step (3) obtains is dissolved, the amination Graphene obtained with step (1) heated and stirred 12h in 77 DEG C of oil baths.The product dehydrated alcohol repetitive scrubbing several obtained, dry 12h.Obtain the Graphene with DOPO group.
Embodiment 4
(1) 0.6g graphite oxide is dissolved in ultrasonic disperse in toluene solution, adds 55ml diethylenetriamine, the Dicyclohexylcarbodiimide (DCC) of 3.6g, stirring and refluxing 9h in the oil bath of 71 DEG C.Reaction terminate after, filter, then with toluene solution repetitive scrubbing until excessive triethylene tetramine solution all washes away.
(2) under nitrogen protection in four-hole boiling flask, add 12gDOPO and 300mL chlorobenzene, heated and stirred, to 73 DEG C, after DOPO is dissolved in chlorobenzene completely, adds 5g benzoquinones in 1.5h, afterwards stirring reaction 2h at 90 DEG C.Gained throw out is cooled to room temperature to filter, chlorobenzene washing for several times, obtains white powder after drying, then heavily ties product with ethanol, can obtain white solid after drying.
In the four-hole boiling flask that (3) 33 g white solids and 125mL epoxy chloropropane add, add KOH(0.5mol/L) as catalyzer, at 70 DEG C of reaction 21h.By products therefrom methanol wash several, after drying, obtain the DOPO with epoxy group(ing).
(4) the epoxide group DOPO that step (3) obtains is dissolved, the amination Graphene obtained with step (1) heated and stirred 12h in 76 DEG C of oil baths.The product dehydrated alcohol repetitive scrubbing several obtained, dry 12h.Obtain the Graphene with DOPO group.
Embodiment 5
(1) 0.7g graphite oxide is dissolved in ultrasonic disperse in DMF solution, adds 70ml quadrol, the Dicyclohexylcarbodiimide (DCC) of 4g, stirring and refluxing 15h in the oil bath of 75 DEG C.Reaction terminate after, filter, then with DMF solution repetitive scrubbing until excessive ethylenediamine solution all washes away.
(2) under nitrogen protection in four-hole boiling flask, add 12gDOPO and 300mL toluene, heated and stirred, to 71 DEG C, after DOPO is dissolved in toluene completely, adds 5g benzoquinones in 1.5h, afterwards stirring reaction 2.5h at 90 DEG C.Gained throw out is cooled to room temperature to filter, toluene wash for several times, obtains white powder after drying, then heavily ties product with ethanol, can obtain white solid after drying.
(3), in the four-hole boiling flask that 34g white solid and 150mL epoxy chloropropane add, NaOH(0.5mol/L is added) as catalyzer, at 65 DEG C of reaction 24h.By products therefrom methanol wash several, after drying, obtain the DOPO with epoxy group(ing).
(4) the epoxide group DOPO that step (3) obtains is dissolved, the amination Graphene obtained with step (1) heated and stirred 12h in 80 DEG C of oil baths.The product dehydrated alcohol repetitive scrubbing several obtained, dry 12h.Obtain the Graphene with DOPO group.
Above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all spirit according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (8)
1. the Graphene containing DOPO group, described DOPO is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and it is characterized in that described Graphene makes graphenic surface with one or more DOPO groups by graft reaction, its structure is as follows:
Wherein: R is phenyl or methylene radical, n >=2.
2. the Graphene containing DOPO group according to claim 1, is characterized in that described phenyl is
or or in one, described methylene radical is-CH
2-or, X>=2.
3. a preparation method for the Graphene containing DOPO group as claimed in claim 1, is characterized in that concrete steps are as follows:
(1) graphite oxide is dissolved in solvent, utilizes ultrasonic disperse, add diamines and Dicyclohexylcarbodiimide, stirring and refluxing 8 ~ 24h in the oil bath of 65 ~ 85 DEG C; After reaction terminates, filter, repetitive scrubbing; Wherein: graphite oxide and diamines weight ratio are 1:150, the weight ratio of diamines and Dicyclohexylcarbodiimide is 1:100;
(2) under nitrogen protection in four-hole boiling flask, add DOPO and solvent, heated and stirred, to 70 ~ 85 DEG C, after DOPO dissolves completely, adds para benzoquinone in 1.5h, and DOPO and benzoquinones weight ratio are 1:150, stirring reaction 2 ~ 4h at 90 DEG C; Gained throw out is cooled to room temperature to filter, washing for several times, obtains white powder after drying, then uses solvent recrystallization, can obtain white solid after drying;
(3), in the four-hole boiling flask white solid obtained in step (2) and epoxy chloropropane added according to weight ratio 1:150, proper catalyst is added, at 65 ~ 75 DEG C of reaction 18 ~ 24h; By products therefrom washing for several times, the DOPO with epoxy group(ing) is obtained after drying;
(4) dissolved by the epoxide group DOPO that step (3) obtains, the amination Graphene obtained with step (1) is according to weight ratio 1:150 heated and stirred 12h in 70 ~ 85 DEG C of oil baths; The product solvent repetitive scrubbing several obtained, dry 12h; Obtain the Graphene with DOPO group.
4., according to the preparation method of a kind of Graphene containing DOPO group described in claim 3, it is characterized in that the Graphene applied comprises individual layer and multi-layer graphene.
5., according to the preparation method of a kind of Graphene containing DOPO group described in claim 3, it is characterized in that described in step (3), diamine structures formula is as follows:
Wherein R is phenyl or methylene radical, n >=2.
6., according to the preparation method of a kind of Graphene containing DOPO group described in claim 3, it is characterized in that one or more that solvent described in step (2), (3) and (4) comprises in methyl alcohol, ethanol, propyl alcohol, dimethyl sulfoxide (DMSO), benzene,toluene,xylene, methylene dichloride, chloroform, acetone, butanone, tetrahydrofuran (THF) or dimethyl formamide.
7. the preparation method of a kind of Graphene containing DOPO group according to claim 3, is characterized in that the weight ratio using the amount of solvent should meet Graphene and solvent or DOPO and solvent described in step (1), (2), (3) and (4) is 1 ~ 150.
8., according to the preparation method of a kind of Graphene containing DOPO group described in claim 3, it is characterized in that catalyzer described in step (3) is one or more in sodium methylate, potassium hydroxide or sodium hydroxide.
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| CN111690172A (en) * | 2020-06-29 | 2020-09-22 | 衡阳师范学院 | Inorganic-organic DOPO-containing flame retardant and preparation method and application thereof |
| CN111690172B (en) * | 2020-06-29 | 2022-05-27 | 衡阳师范学院 | Inorganic-organic DOPO-containing flame retardant and preparation method and application thereof |
| CN114426701A (en) * | 2022-01-11 | 2022-05-03 | 桂林理工大学 | Preparation of P-N compound and graphene oxide synergistic flame retardant and application of P-N compound and graphene oxide synergistic flame retardant in epoxy resin |
| CN114426701B (en) * | 2022-01-11 | 2023-08-15 | 桂林理工大学 | Preparation of P-N compound synergistic graphene oxide flame retardant and application of P-N compound synergistic graphene oxide flame retardant in epoxy resin |
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Application publication date: 20151028 |