CN105037801A - Phosphorus-containing hybridization graphene oxide and preparation method thereof - Google Patents
Phosphorus-containing hybridization graphene oxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses phosphorus-containing hybridization graphene oxide and a preparation method thereof. Graphene oxide reacts with phosphazene to obtain phosphazene modified graphene oxide, a silane coupling agent is added, and water is added dropwise, so that the silane coupling agent undergoes hydrolysis and hyperbranch; and after the reaction is ended, through filtration, washing and drying, the phosphorus-containing hybridization graphene oxide with the phosphorous content of 1.1-11.0 wt% is obtained. The agglomeration phenomenon of the prepared phosphorus-containing hybridization graphene oxide is improved compared with graphene oxide, and the phosphorus-containing hybridization graphene oxide has excellent heat stability and flame retardant property. On the basis of basically maintaining original outstanding dielectric properties of cyanate ester, the problems that in the prior art, the starting thermal destruction temperature of phosphorus-containing flame retardant modified thermosetting resin is lowered and the starting ignition time is shortened are solved. Besides, the phosphorus content of the phosphorus-containing hybridization graphene oxide is obviously lower than that of a similar material reported in literature. The preparation method is simple and practical, raw materials can be obtained easily, and the applicability is wide.
Description
Technical field
The present invention relates to a kind of inorganic combustion inhibitor and preparation method thereof, particularly phosphorous hydridization graphene oxide of one and preparation method thereof.
Background technology
" fire-retardant " has become the indispensable performance of numerous leading-edge fields macromolecular material.But nearly all organic materials does not have good flame retardant resistance.The effective ways preparing flame retarded polymeric material at present add fire retardant.Phosphorus flame retardant (PFRs) is widely used kind in current halogen-free flame retardants, but, when PFRs adds heat-resisting thermosetting resin, usually reduce the initial heat decomposition temperature (Tdi) of resin and initial burning time (TTI) is shortened.In addition, recent research shows, and PFRs exists bioconcentration, influence ecological environment and human health.Therefore, how on the basis not reducing resin proper property, the environment-friendlyflame flame retardant that exploitation is applicable to the low phosphorus content of heat-resisting thermosetting resin becomes a challenging significant problem.
In order to overcome the problem that TTI shortens, at present, the thinking that people deal with problems is mixed with the material of good heat resistance by P contained compound.Such as, document (WenchaoZhang, XiangmeiLi, HaiboFan, RongjieYang, PolymerDegradationandStability2012, 97(11), 2241-2248) report nitric acid acidification is carried out to octaphenyl eight silicious sesquioxane, obtain eight amino-benzene odaaps (OAPS), by the technical scheme joined together with OAPS with DOPO in epoxy (EP) resin, but it only reports EP/DOPO/OAPS mass ratio is the result of study of flame retardant resistance under 94.6/3.1/2.3 and thermal characteristics, show: with EP resin-phase ratio, the TTI of EP/DOPO/OAPS resin extends about 8s, but its Tdi reduces.
In order to overcome the problem that thermotolerance reduces, people adopt the composite of DOPO P contained compound and more function group material, the product that formation molecular weight is larger.There is bibliographical information that DOPO and hyperbranched polyorganosiloxane reaction are generated P-HSi, by its modification CE resin, and result of study (JuhuaYe, GuozhengLiang, the AijuanGu of the thermal characteristics disclosed when P-HSi consumption is at 5wt% ~ 35wt% and flame retardant resistance, ZhiyongZhang, JipengHan, LiYuan, PolymerDegradationandStability2013,98(2), 597-608).Result shows, and the Tdi of modified system is all high than the value of CE resin, and under 5wt%P-HSi addition, the P content of resin system is 1.8wt%, and limiting oxygen index(LOI) (LOI) is increased to 37 from 27, but its TTI does not make a search.Also have literature research heat-resisting hyperbranched polyorganosiloxane and DOPO hydridization (ZhiyongZhang, LiYuan, ZhixiangQiang, GuozhengLiang, AijuanGu, Industrial & EngineeringChemistryResearch2015,54 (3), 938-948), and prepare new phosphorus-containing flame retardant EPHSi, investigate the thermal characteristics of 1.5wt% and 2.5wt%EPHSi on CE resin and the impact of flame retardant resistance.Result of study shows, with CE resin-phase ratio, the TTI of EPHSi modification CE resin shortens about 10 ~ 20s, and Tdi is all lower than the value of pure CE resin, and maximum heat rate of release (PHRR) is close with pure CE resin, therefore, DOPO and more function group material is composite does not reach the problem overcoming phosphonium flame retardant and thermosetting resin TTI is shortened.
In order to reach the object reducing phosphorus (P) content, people adopt the method for phosphonium flame retardant and inorganic nano-material hybrid.Bibliographical information with phosphorus oxychloride and tetramethylolmethane for reactant has prepared hydridization expanded graphite (hIFR), and prepared hIFR modification CE resin (JipengHan, GuozhengLiang, AijuanGu, JuhuaYe, ZhiyongZhangandLiYuanJ.Mater.Chem.A2013,1(6), 2169-2182), have studied the thermal characteristics under 5wt%, 10wt%, 15wt%, 20wt% addition, find that the Tdi containing the hIFR modification CE resin of 5 ~ 15wt% promotes, the Tdi of 20wt% modification CE resin slightly falls.The document has only carried out flame retardant properties research to the modification CE resin containing 5wt%hIFR, and its maximum heat rate of release (PHRR) reduces 32.3%, and now phosphorus content is 0.05wt%, but its TTI but shortens nearly 60s.Separately there is document to also disclose, with hexachlorocyclotriphosphazene, CPBN is obtained to boron nitride modification, for carrying out flame-retardant modified (WenqinJin to bismaleimides (BD), LiYuan, GuozhengLiang, andAijuanGu, ACSappliedmaterials & interfaces2014, 6(17), 14931-14944), have studied flame retardant resistance and the thermal characteristics of CPBN addition CPBN/BD when 5wt% and 10wt%, result shows, TTI is delayed 88s and 96s respectively, PHRR reduces by 40.9% respectively, 45.9%, but modified system Tdi reduces 11.6 DEG C and 31.3 DEG C respectively.The people such as Hu (WeizhaoHu, LeiSong, JianWang, YuanHu, PingZhang, FireSafetyScience2014,11,191-191) adopt DOPO and benzoquinones (BQ) to be obtained by reacting DOPO-BQ, obtain PDBMP with dichloromethyl phosphine reaction again, be grafted on graphene oxide, obtain FGO.With the FGO modified epoxy of 1wt% and 2wt% in research, while raising flame retardant resistance, the TTI of all modified epoxy systems shortens and Tdi reduces.The people such as Wang (ZehaoWang, PingWei, YongQian, JipingLiu, Compos.Pt.B-Eng.2014,60,341-349) adopt sol-gel method to make phosphenyl oxychloride and APTES reaction, then be grafted to graphene oxide, prepare modified graphene oxide (GFR).GFR is joined in epoxy resin according to 0.5wt%, 1.0wt, 2.0wt%.Only be studied the flame retardant resistance of 1wt%GFR modified epoxy in literary composition, result shows, and LOI is promoted to 24, PHRR by 20 and reduces 44.7%, but all modified epoxies all shorten than the TTI of pure epoxy resin.Also there is bibliographical information to prepare hyperbranched polyorganosiloxane and combine hydridization multi-walled carbon nano-tubes (EPHSi-g-MWCNT) with DOPO, the flame retardant properties of research EPHSi-g-MWCNT content modification CE resin and dielectric properties.Research finds, along with the increase of EPHSi-g-MWCNT content, the flame retardant resistance of modification CE resin is improved amplitude and is increased, but specific inductivity and loss but significantly raise (ZhiyongZhang, LiYuan, ZhixiangQiang, GuozhengLiang, AijuanGu, Industrial & EngineeringChemistryResearch2015,54 (3), 938-948) advantage of CE resin low-k, is seriously lost.
These research work above-mentioned overcome one or two problems that PFRs exists in heat-resisting thermosetting resin application, and do not solve TTI and Tdi problem simultaneously.In addition, the excellent properties of not sacrificing unmodified resin is the prerequisite of all material study on the modification.
On the other hand, environmental protection and healthy in problem also become the new focus of concern.The research and development of BACN should comprise low phosphorus content.The people such as Gao are at research 1-oxygen base phospha-4-methylol-2, 6, during the flame retardant effect of microcapsule-type fire retardant to epoxy resin of 7-trioxa-l-phosphabicyclo [2.2.2] octane and phosphorus oxychloride composition, be only 0.96wt% to phosphorus content in modified resin, 1.44wt%, the system of 1.92wt% and 2.40wt% is studied (MingGao, YaqiWo, WeihongWu, J.Appl.Polym.Sci.2011, 119(4), 2025-2030), find that phosphorus content occurs flame retardant effect from 1.44wt%, but only Thermal Properties is carried out to phosphorus content modified resin under 1.92wt% in literary composition, result shows its Tdi and reduces.The people such as Zhao (WeiZhao, JipingLiu, HuiPeng, JiayingLiao, XiaojunWang, PolymerDegradationandStability2015,118(0), 120-129) after 1-oxygen base phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane and phosphorus oxychloride reaction, introduce 4,4 '-diaminodiphenylsulfone(DDS) synthesis fire retardant (PSA), joins PSA in epoxy resin, the flame retardant properties of research phosphorus content under 0.64 ~ 2.56wt%.In modified epoxy, the LOI of phosphorus content material when 1.28wt% is increased to 28.0, UL94 from 24.7 is V-1 level, but all modified systems all exist the problem that TTI shortens and Tdi reduces.The people such as Xu (MiaojunXu, WeiZhao, BinLi, KunYang, LiLin, FireMater.doi:10.1002/fam.2252) synthesize oil of mirbane benzene phosphorus oxygen base oligopolymer, have studied the flame retardant resistance of phosphorus content between 0.6wt%-2.7wt%, in modified resin, phosphorus content has flame retardant resistance from 1.2wt%, but the problem that all modified systems all have Tdi to reduce.
In sum, when being applied to thermosetting resin and being flame-retardant modified, the problem that existing phosphonium flame retardant ubiquity TTI shortens and Tdi reduces; Meanwhile, phosphorus content is generally relatively high.
Summary of the invention
The present invention is directed to existing phosphonium flame retardant for deficiency existing during modified heat resistant thermosetting resin, there is provided a kind of on the basic basis keeping the original outstanding dielectric properties of cyanate ester resin, low-phosphorous addition, can realize postponing TTI and the phosphorous hydridization graphene oxide improving Tdi and preparation method thereof simultaneously.
To achieve the above object of the invention, the technical solution adopted in the present invention is to provide a kind of preparation method of phosphorous hydridization graphene oxide, comprises the steps: by mass,
(1) 1 part of graphene oxide is fully mixed with 500 ~ 1000 parts of tetrahydrofuran (THF)s, obtain system A; Under protection of inert gas and agitation condition, 10 ~ 50 parts of triethylamines are joined in system A, be react 0.5 ~ 2h under the condition of 0 ~ 4 DEG C in temperature, obtain system B;
(2) 1 ~ 10 part of phosphonitrile is dissolved in 100 ~ 400 parts of tetrahydrofuran (THF)s, obtains system C; Dropwise being joined by system C in the obtained system B of step (1), is after reacting 1 ~ 5h under the condition of 0 ~ 4 DEG C in temperature, is warming up to isothermal reaction 2 ~ 5h under 40 ~ 70 DEG C of temperature condition, obtains system D;
(3) 20 ~ 50 parts of silane coupling agents are dissolved in 200 ~ 400 parts of tetrahydrofuran (THF)s, obtain system E; Dropwise dropped to by system E in the obtained system D of step (2), under 40 ~ 70 DEG C of temperature condition, isothermal reaction 2 ~ 5h, obtains system F;
(4) 4 ~ 10 parts of water are dropwise joined in the obtained system F of step (3), under 40 ~ 70 DEG C of temperature condition after isothermal reaction 2 ~ 5h, then under 15 ~ 25 DEG C of temperature condition isothermal reaction 10 ~ 24h; After reaction terminates, after filtration, washing, dry, a kind of phosphorous hydridization graphene oxide is obtained.
Silane coupling agent described in technical solution of the present invention is the one in APTES, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, or their arbitrary combination.Described rare gas element is the one in nitrogen or argon gas.
Technical solution of the present invention also comprises the phosphorous hydridization graphene oxide of the one obtained by above-mentioned preparation method.Its phosphorus content is 1.1 ~ 11.0wt%.
Compared with prior art, the beneficial effect acquired by the present invention is:
1, the phosphorous hydridization graphene oxide that prepared by the present invention is combined with phosphorous molecule in the mode of chemical bonding, and joined in thermosetting resin, the Tdi of resin is improved significantly, and overcomes the existing phosphorous problem that resin Tdi is reduced existed from fire retardant.Its principle is: (1) surface of graphene oxide itself is with certain hydroxyl, carboxyl, epoxy group(ing) isoreactivity group, and kind and the quantity of active group have been enriched in the existence of hyperbranched polyorganosiloxane further, give phosphorous hydridization graphene oxide and the good chemical reactivity of interlaminar resin and interface interaction power, form more stable chemical structure; (2) compared with other conventional P contained compounds, the P=N key in phosphonitrile and P-N key have excellent stability; (3) there is the outermost layer of hyperbranched polyorganosiloxane macromole at graphene oxide lamella of outstanding thermotolerance, be conducive to the overall thermotolerance improving resin further; (4) laminated structure of phosphorous hydridization graphene oxide uniqueness, can hinder the transmission of heat.
2, the phosphorous hydridization graphene oxide that prepared by the present invention has efficient flame retardant resistance, and extends TTI.Its principle is: (1) phosphorous hydridization graphene oxide has abundant active group, by active group and resin matrix with chemical bonds, fire retardant can be made to be dispersed in inside resin, be conducive to the performance of flame retardant effect; (2) fire retardant makes modified resin become charcoal ability to increase, thus reaches the effect of cooperative flame retardant; (3) gas that phosphorus containg substances generates enters gas phase, plays gas phase fire retardation; (4) laminated structure of phosphorous hydridization graphene oxide, hinders the transmission of heat and gas, provides good physical barriers, play good flame retardant effect.
3, the phosphorous hydridization graphene oxide that prepared by the present invention has hydroxyl, carboxyl, amino isoreactivity group, for polymer modification and novel material research and development provide good material guarantee.
4, the preparation method of phosphorous hydridization graphene oxide provided by the invention has that material source is wide, technique is simple, be easy to the features such as control.
Accompanying drawing explanation
The infrared spectrum of the phosphorous hydridization graphene oxide that Fig. 1 is graphene oxide, hexachlorocyclotriphosphazene and the embodiment of the present invention 1 provide;
Fig. 2 is the x-ray photoelectron power spectrum of the phosphorous hydridization graphene oxide that graphene oxide and the embodiment of the present invention 1 provide;
Fig. 3 is the C1s spectrogram in the x-ray photoelectron power spectrum of the phosphorous hydridization graphene oxide that the embodiment of the present invention 1 provides;
Fig. 4 is the N1s spectrogram in the x-ray photoelectron power spectrum of the phosphorous hydridization graphene oxide that the embodiment of the present invention 1 provides;
The X-ray diffraction spectrogram of the phosphorous hydridization graphene oxide that the hyperbranched polyorganosiloxane grafting phosphonitrile that Fig. 5 is graphene oxide, comparative example 1 provides and the embodiment of the present invention 1 provide;
The transmission electron microscope of the phosphorous hydridization graphene oxide that Fig. 6 is graphene oxide, the embodiment of the present invention 1 provides and scanning transmission electron microscope figure (STEM);
Fig. 7 is the elemental scan spectrogram of the phosphorous hydridization graphene oxide that inventive embodiments 1 provides;
Fig. 8 is thermal weight loss (TG) graphic representation (under nitrogen atmosphere, temperature rise rate is 10 DEG C/min) of the phosphorous hydridization graphene oxide that graphene oxide and the embodiment of the present invention 1 provide;
Fig. 9 is phosphorous hydridization graphene oxide/cyanate ester resin thermal weight loss (TG) graphic representation (nitrogen atmosphere, temperature rise rate is 10 DEG C/min) that the cyanate ester resin that provides of comparative example 2 of the present invention and comparative example 3 provide;
Figure 10 is the heat release rate-time plot of phosphorous hydridization graphene oxide/cyanate ester resin that the cyanate ester resin that provides of comparative example 2 of the present invention and comparative example 3 provide.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention will be further described.
Embodiment 1
0.1g graphene oxide is added 100g tetrahydrofuran (THF), ultrasonic disperse 1h, obtain well-mixed system A; Under nitrogen protection and agitation condition, 5g triethylamine is joined in system A, at 0 DEG C, react 1h, obtain system B; 1g phosphonitrile is dissolved in 20g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 3 DEG C, reacts 2h; React 3h at being warming up to 60 DEG C again, obtain system D; 3.8g3-aminopropyltriethoxywerene werene is dissolved in 20g tetrahydrofuran (THF), obtains system E; System E is dropwise dropped in system D, at 60 DEG C, reacts 3h, obtain system F; 0.4g water is dropwise joined in system F, at 60 DEG C, reacts 3h; 10h is reacted subsequently at 20 DEG C.After reaction terminates, filter, wash 5 times respectively with tetrahydrofuran (THF) and ethanol, in 60 DEG C of vacuum drying ovens after dry 10h, namely obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 11wt%.The transmission electron microscope of the C1s spectrum in its infrared spectrum, x-ray photoelectron power spectrum, x-ray photoelectron power spectrum, the N1s spectrum in x-ray photoelectron power spectrum, X-ray diffraction spectrum, amplification 15,000 times and surface sweeping transmission electron microscope picture, elemental scan spectrogram and thermal weight loss (TG) curve are respectively see accompanying drawing 1,2,3,4,5,6,7 and 8.
See accompanying drawing 1, the infrared spectrum of the phosphorous hydridization graphene oxide that it is graphene oxide, hexachlorocyclotriphosphazene and the embodiment of the present invention 1 provide.Comparison is found out, does not occur the charateristic avsorption band (601cm of P-Cl key in phosphorous hydridization graphene oxide spectrogram
-1), prove that the chlorine element in phosphonitrile is fully substituted.In addition, there is P-O-C key (949cm in phosphorous hydridization graphene oxide spectrogram
-1), Si-O key (1121cm
-1), P-N key (1208cm
-1), C=C key (1621cm
-1), C=O key (1707cm
-1) and CH
2(2931cm
-1) absorption peak, prove that phosphonitrile and hyperbranched polyorganosiloxane are successfully grafted on graphene oxide.
See accompanying drawing 2, it is the x-ray photoelectron power spectrum of the phosphorous hydridization graphene oxide that graphene oxide and the embodiment of the present invention 1 provide.In the wide range scanning of graphene oxide, at the absorption peak of corresponding C1s and O1s of absorption peak difference at combination energy 284eV and 529eV place.Compare the spectrogram of graphene oxide, there is Si2p(102eV in the wide range scanning of phosphorous hydridization graphene oxide), P2p(132eV), P2s(192.2eV), N1s(398eV) new absorption peak, illustrate that phosphonitrile and hyperbranched polyorganosiloxane have successfully been grafted on graphene oxide.Its concrete constituent content is in table 1, and the mass ratio shared in phosphorous hydridization graphene oxide according to each element, can calculate phosphorus content under 1.0wt% addition is 0.10wt%, and result is see table 1.
The ratio of each element in table 1 phosphorous hydridization graphene oxide
See accompanying drawing 3, it is the C1s spectrogram in the x-ray photoelectron power spectrum of the phosphorous hydridization graphene oxide that the present embodiment provides.C=C(284.4eV can be represented respectively by swarming curve), C-O(286.2eV), C=O(287.0eV), O-C=O(288.5eV), C-O-P(285.7eV) and peak C-N(285.1eV), illustrate that phosphonitrile and hyperbranched polyorganosiloxane are grafted on graphene oxide.
See accompanying drawing 4, it is the N1s spectrogram in the x-ray photoelectron power spectrum of the phosphorous hydridization graphene oxide that the present embodiment provides.According to the phosphorous chemical structure of hydridization graphene oxide and the analysis diagram of N1s thereof, spectrogram exists ,-N-H-(400.7eV) ,-N=P-(401.4eV) and-N-C(398.9eV) peak of structure.In conjunction with infrared spectrum and x-ray photoelectron power spectrum, can find out that phosphonitrile and hyperbranched polyorganosiloxane have been grafted on graphene oxide, namely phosphorous hydridization graphene oxide successfully synthesizes.
Comparative example 1, the preparation of hyperbranched polyorganosiloxane grafting phosphonitrile: 1g phosphonitrile is dissolved in 20g tetrahydrofuran (THF) and obtains system A; 3.8g3-aminopropyltriethoxywerene werene is dissolved in 20g tetrahydrofuran (THF), obtains system B; In nitrogen protection, under mechanical agitation, system B is dropwise dropped in system A, at 60 DEG C, react 3h; 10h is reacted subsequently under 20 DEG C of temperature condition.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 5 times, 60 DEG C vacuum drying ovens drying 10h after, obtain hyperbranched polyorganosiloxane grafting phosphonitrile, its X-ray diffraction spectrogram is see accompanying drawing 5.
See accompanying drawing 5, the X-ray diffraction spectrogram of the phosphorous hydridization graphene oxide that the hyperbranched polyorganosiloxane grafting phosphonitrile that it is graphene oxide, comparative example 1 provides and the embodiment of the present invention 1 provide.In the XRD figure of hyperbranched polyorganosiloxane grafting phosphonitrile prepared by comparative example 1, the diffraction peak of left and right, 2 θ=21.40 ° appearance comes from phosphonitrile and the reacted amino substituents of hyperbranched polyorganosiloxane.The XRD spectra of the graphene oxide in embodiment 1 and phosphorous hydridization graphene oxide respectively in 2 θ=10.00 ° and a ° place, 2 θ=9.72 there is (002) diffraction peak, 0.88nm and 0.91nm can be respectively in the hope of interlamellar spacing (d) value of graphene oxide and phosphorous hydridization graphene oxide.The interlamellar spacing of phosphorous hydridization graphene oxide is greater than the interlamellar spacing of graphene oxide, and further demonstrate hyperbranched polyorganosiloxane and be grafted on graphene oxide, the aggregate structure of graphene oxide lamella improves.
See accompanying drawing 6, the transmission electron microscope of the phosphorous hydridization graphene oxide that it is graphene oxide, the present embodiment provides and scanning transmission electron microscope figure.Wherein, and 3. 1. figure is respectively transmission electron microscope and the scanning transmission electron microscope figure (STEM) that graphene oxide amplifies 2,000 times, and the phosphorous hydridization graphene oxide that 2. and 4. figure is respectively the present embodiment and provides amplifies transmission electron microscope and the scanning transmission electron microscope figure (STEM) of 15,000 times.See accompanying drawing 7, it is the elemental scan spectrogram of the phosphorous hydridization graphene oxide that the present embodiment provides, and is the accompanying drawing 6 4. Surface scan spectrogram of C/O/P/Si element in graph region.In comparison diagram 6 1. and 2. known, grafting material on hydridization rear oxidation Graphene, from the vegetarian noodles surface sweeping of Fig. 7 unit, 4 kinds of elements such as C, O, P, Si are evenly distributed in sample surfaces, show that grafts contains this four kinds of elements.Comprehensive accompanying drawing 1 ~ 7 is known, and phosphorous hydridization graphene oxide successfully synthesizes.
See accompanying drawing 8, it is thermal weight loss (TG) curve (under nitrogen atmosphere, temperature rise rate is 10 DEG C/min) of the phosphorous hydridization graphene oxide that graphene oxide and the present embodiment provide.As seen from the figure, the Tdi of graphene oxide and phosphorous hydridization graphene oxide is respectively 195 DEG C and 213 DEG C, show that the thermostability of phosphorous hydridization graphene oxide is higher than graphene oxide, this key factor has more stable chemical structure in phosphorous hydridization graphene oxide.
Comparative example 2, the preparation of cyanate ester resin: by two to 50g2,2'-(4-cyanogen oxygen phenyl) propane (bisphenol-A-type cyanate) ultrasonic agitation 0.5h at 80 DEG C, then stir 6h at 190 DEG C, obtain cyanate ester resin prepolymer; This prepolymer is poured in mould, and at 190 DEG C, carries out the degassed of 15min under vacuo and pressurize 0.5h.Afterwards, be cured and thermal treatment according to the technique of 200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h, obtain cyanate ester resin.Its TG curve and heat release rate in time variation diagram respectively see accompanying drawing 8 and 9.
Comparative example 3, the preparation of phosphorous hydridization graphene oxide/cyanate ester resin: phosphorous hydridization graphene oxide prepared by 0.50g embodiment 1 and 49.50g2, two (4-cyanogen oxygen phenyl) the propane resin of 2'-, ultrasonic agitation 0.5h at 80 DEG C, then at 190 DEG C, stir 6h, obtain phosphorous hydridization graphene oxide/cyanate ester resin prepolymer; This prepolymer is poured in mould, and at 190 DEG C, carries out the degassed of 15min under vacuo and pressurize 0.5h.Afterwards, be cured and thermal treatment according to the technique of 200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h, obtain phosphorous hydridization graphene oxide/cyanate ester resin.Its TG curve and heat release rate in time variation diagram are shown in accompanying drawing 8 and 9 respectively.
See accompanying drawing 9, the TG curve (nitrogen atmosphere, temperature rise rate is 10 DEG C/min) of the cyanate ester resin that it provides for comparative example 2 and phosphorous hydridization graphene oxide/cyanate ester resin that comparative example 3 provides.As seen from the figure, the Tdi of phosphorous hydridization graphene oxide/cyanate ester resin improves 18.8 DEG C compared with the Tdi of cyanate ester resin, shows that phosphorous hydridization graphene oxide/cyanate ester resin has better thermostability.
See accompanying drawing 10, the heat release rate variation diagram in time of the cyanate ester resin that it provides for comparative example 2 and phosphorous hydridization graphene oxide/cyanate ester resin that comparative example 3 provides.As seen from the figure, the TTI of phosphorous hydridization graphene oxide/cyanate ester resin comparatively cyanate ester resin is delayed 31s, and PHRR reduces 40.1%.Under this content, the LOI of phosphorous hydridization graphene oxide/cyanate ester resin be 29.8 comparatively cyanate ester resin promote 14.6%, only to have at phosphoric under the content of 0.1wt% flame retardant properties comparatively cyanate have and significantly promote; Now, when frequency is at 1Hz, specific inductivity is 3.6, and dielectric loss is for being 0.0056, close with cyanate ester resin (specific inductivity 3.3, dielectric loss is 0.0063), maintains the dielectric properties of original cyanate ester resin excellence.
Can reach a conclusion based on above performance data, the agglomeration of phosphorous hydridization graphene oxide prepared by the present invention comparatively graphene oxide improves, and has excellent thermostability and flame retardant properties.On the basic basis keeping the original outstanding dielectric properties of cyanate ester resin, solve in prior art, the Tdi that phosphonium flame retardant modified heat convertible resin exists reduces the problem shortened with TTI, and phosphorus content is only 12.0 ~ 26.3% of report value in similar document.
Embodiment 2
0.1g part graphene oxide is added 50g tetrahydrofuran (THF), mechanical stirring 50min, obtains well-mixed system A; Under argon shield and agitation condition, 1g triethylamine is joined in system A, at 0 DEG C, react 0.5h, obtain system B; 0.1g phosphonitrile is dissolved in 10g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 4 DEG C, reacts 1h; React 2h at being warming up to 40 DEG C again, obtain system D; 2g γ-aminopropyltrimethoxysilane is dissolved in 10g tetrahydrofuran (THF), obtains system E; System E is dropwise dropped in system D, under 45 DEG C of conditions, reacts 2h, obtain system F; 0.4g water is dropwise joined in system F, at 60 DEG C, reacts 2h under condition; 10h is reacted subsequently at 15 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 5 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 1.1wt%.
Embodiment 3
0.1g graphene oxide is added 100g tetrahydrofuran (THF), ultrasonic disperse 1h, obtain well-mixed system A; Under nitrogen protection and agitation condition, 5g triethylamine is joined in system A, at 4 DEG C, react 2h, obtain system B; 0.35g phosphonitrile is dissolved in 40g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 2 DEG C, reacts 5h; React 5h at being warming up to 70 DEG C again, obtain system D; 5g γ-aminopropyltriethoxy diethoxy silane is dissolved in 40g tetrahydrofuran (THF), obtains system E; System E is dropwise dropped in system D, at 45 DEG C, reacts 5h, obtain system F; 1g water is dropwise joined in system F, at 55 DEG C, reacts 5h; 24h is reacted subsequently at 25 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 5 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 3.9wt%.
Embodiment 4
0.1g graphene oxide is added 70g tetrahydrofuran (THF), and high speed machine stirs 45min, obtains well-mixed system A; Under argon shield and agitation condition, 3g triethylamine is joined in system A, at 3 DEG C, react 1h, obtain system B; 0.76g phosphonitrile is dissolved in 20g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 0 DEG C, reacts 3h; React 3h at being warming up to 55 DEG C again, obtain system D; 1g γ-aminopropyltrimethoxysilane and 4g γ-aminopropyltriethoxy diethoxy silane are dissolved in 40g tetrahydrofuran (THF), obtain system E; System E is dropwise dropped in system D, at 62 DEG C, reacts 3h, obtain system F; 0.8g water is dropwise joined in system F, at 70 DEG C, reacts 3h; 10h is reacted subsequently at 15 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 5 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 8.4wt%.
Embodiment 5
0.1g graphene oxide is added 70g tetrahydrofuran (THF), ultrasonic disperse 70min, obtain well-mixed system A; Under nitrogen and agitation condition, 1g triethylamine is joined in system A, at 2 DEG C, react 0.5h, obtain system B; 0.27g phosphonitrile is dissolved in 20g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 4 DEG C, reacts 5h; React 3h at being warming up to 49 DEG C again, obtain system D; 2.5g γ-aminopropyltrimethoxysilane is dissolved in 20g tetrahydrofuran (THF), obtains system E; System E is dropwise dropped in system D, at 40 DEG C, reacts 5h, obtain system F; 1g water is dropwise joined in system F, at 55 DEG C, reacts 5h; 24h is reacted subsequently at 23 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 5 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 3.0wt%.
Embodiment 6
0.1g graphene oxide is added 80g tetrahydrofuran (THF), ultrasonic disperse 1h, obtain well-mixed system A; Under argon gas and agitation condition, 5g triethylamine is joined in system A, at 3 DEG C, react 1h, obtain system B; 0.8g phosphonitrile is dissolved in 40g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 2 DEG C, reacts 5h; React 5h at being warming up to 48 DEG C again, obtain system D; 2.8g γ-aminopropyltriethoxy diethoxy silane is dissolved in 40g tetrahydrofuran (THF), obtains system E; System E is dropwise dropped in system D, at 70 DEG C, reacts 5h, obtain system F; 0.8g water is dropwise joined in system F, at 62 DEG C, reacts 2h; 20h is reacted subsequently at 23 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 5 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 8.8wt%.
Embodiment 7
0.1g graphene oxide is added 100g tetrahydrofuran (THF), mechanical stirring 1h, obtain well-mixed system A; Under nitrogen protection and agitation condition, 5g triethylamine is joined in system A, at 0 DEG C, react 1h, obtain system B; 0.64g phosphonitrile is dissolved in 20g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 4 DEG C, reacts 5h; React 5h at being warming up to 60 DEG C again, obtain system D; 2.5g3-aminopropyltriethoxywerene werene and 2.5g γ-aminopropyltriethoxy diethoxy silane are dissolved in 20g tetrahydrofuran (THF), obtain system E; System E is dropwise dropped in system D, at 68 DEG C, reacts 5h, obtain system F; 1g water is dropwise joined in system F, at 58 DEG C, reacts 3h; 24h is reacted subsequently at 25 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 5 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 7.0wt%.
Embodiment 8
0.1g graphene oxide is added 50g tetrahydrofuran (THF), ultrasonic disperse 1h, obtain well-mixed system A; Under nitrogen protection and agitation condition, 1g triethylamine is joined in system A, at 3 DEG C, react 2h, obtain system B; 0.37g phosphonitrile is dissolved in 20g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 0 DEG C, reacts 2h; React 3h at being warming up to 56 DEG C again, obtain system D; 2g3-aminopropyltriethoxywerene werene, 1g γ-aminopropyltrimethoxysilane and 2g γ-aminopropyltriethoxy diethoxy silane are dissolved in 20g tetrahydrofuran (THF), obtain system E; System E is dropwise dropped in system D, at 48 DEG C, reacts 3h, obtain system F; 0.4g water is dropwise joined in system F, at 70 DEG C, reacts 3h; 10h is reacted subsequently at 27 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 4 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 4.1wt%.
Embodiment 9
0.1g graphene oxide is added 100g tetrahydrofuran (THF), mechanical stirring 1h, obtain well-mixed system A; Under nitrogen protection and agitation condition, 5g triethylamine is joined in system A, at 4 DEG C, react 2h, obtain system B; 0.9g phosphonitrile is dissolved in 20g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 0 DEG C, reacts 3h; React 5h at being warming up to 46 DEG C again, obtain system D; 1g3-aminopropyltriethoxywerene werene and 3g γ-aminopropyltrimethoxysilane are dissolved in 20g tetrahydrofuran (THF), obtain system E; System E is dropwise dropped in system D, at 50 DEG C, reacts 3h, obtain system F; 0.8g water is dropwise joined in system F, at 55 DEG C, reacts 5h; 18h is reacted subsequently at 15 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 3 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 9.9wt%.
Embodiment 10
0.1g graphene oxide is added 100g tetrahydrofuran (THF), ultrasonic disperse 1h, obtain well-mixed system A; Under nitrogen protection and agitation condition, 5g triethylamine is joined in system A, at 4 DEG C, react 2h, obtain system B; 0.23g phosphonitrile is dissolved in 40g tetrahydrofuran (THF), obtains system C; System C is dropwise joined in system B, at 2 DEG C, reacts 5h; React 5h at being warming up to 70 DEG C again, obtain system D; 5g γ-aminopropyltriethoxy diethoxy silane is dissolved in 40g tetrahydrofuran (THF), obtains system E; System E is dropwise dropped in system D, at 45 DEG C, reacts 5h, obtain system F; 1g water is dropwise joined in system F, at 55 DEG C, reacts 5h; 24h is reacted subsequently at 25 DEG C.Reaction terminate after, wash respectively after filtration, with tetrahydrofuran (THF) and ethanol 5 times, 60 DEG C vacuum drying ovens drying 10h after, obtain phosphorous hydridization graphene oxide, wherein phosphorus content is 2.5wt%.
Claims (5)
1. a preparation method for phosphorous hydridization graphene oxide, is characterized in that comprising the steps: by mass,
(1) 1 part of graphene oxide is fully mixed with 500 ~ 1000 parts of tetrahydrofuran (THF)s, obtain system A; Under protection of inert gas and agitation condition, 10 ~ 50 parts of triethylamines are joined in system A, be react 0.5 ~ 2h under the condition of 0 ~ 4 DEG C in temperature, obtain system B;
(2) 1 ~ 10 part of phosphonitrile is dissolved in 100 ~ 400 parts of tetrahydrofuran (THF)s, obtains system C; Dropwise being joined by system C in the obtained system B of step (1), is after reacting 1 ~ 5h under the condition of 0 ~ 4 DEG C in temperature, rises to isothermal reaction 2 ~ 5h under 40 ~ 70 DEG C of temperature condition, obtains system D;
(3) 20 ~ 50 parts of silane coupling agents are dissolved in 200 ~ 400 parts of tetrahydrofuran (THF)s, obtain system E; Dropwise dropped to by system E in the obtained system D of step (2), under 40 ~ 70 DEG C of temperature condition, isothermal reaction 2 ~ 5h, obtains system F;
(4) 4 ~ 10 parts of water are dropwise joined in the obtained system F of step (3), under 40 ~ 70 DEG C of temperature condition after isothermal reaction 2 ~ 5h, then under 15 ~ 25 DEG C of temperature condition isothermal reaction 10 ~ 24h; After reaction terminates, after filtration, washing, dry, a kind of phosphorous hydridization graphene oxide is obtained.
2. the preparation method of a kind of phosphorous hydridization graphene oxide according to claim 1, it is characterized in that: described silane coupling agent is the one in APTES, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, or their arbitrary combination.
3. the preparation method of a kind of phosphorous hydridization graphene oxide according to claim 1, is characterized in that: described rare gas element is the one in nitrogen or argon gas.
4. by the phosphorous hydridization graphene oxide of one that claim 1 preparation method obtains.
5. the phosphorous hydridization graphene oxide of one according to claim 4, is characterized in that: the phosphorus content of phosphorous hydridization graphene oxide is 1.1 ~ 11.0wt%.
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