CN102585291A - Surface modified carbon nanotube and preparation method thereof - Google Patents
Surface modified carbon nanotube and preparation method thereof Download PDFInfo
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- CN102585291A CN102585291A CN2012100216806A CN201210021680A CN102585291A CN 102585291 A CN102585291 A CN 102585291A CN 2012100216806 A CN2012100216806 A CN 2012100216806A CN 201210021680 A CN201210021680 A CN 201210021680A CN 102585291 A CN102585291 A CN 102585291A
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Abstract
The invention discloses a surface modified carbon nanotube and a preparation method thereof and relates to the inorganic nanotube technology. Hyperbranched polysiloxane containing phosphaphenanthrene structures and amino groups, epoxy functionalized carbon nanotubes and catalysts of triphenylphosphine are mixed, then, the obtained mixture is added into solvents, the ultrasonic treatment is carried out, the solvents are removed after the reaction completion, and the surface modified carbon nanotube connected with the phosphaphenanthrene structures and the amino groups in the chemical bond mode is obtained. The surface modified carbon nanotube contains a plurality of amino groups, so good dispersion in thermosetting resin can be realized, and meanwhile, good flame resistance and good toughness are given to the thermosetting resin on the basis of keeping the heat resistance and the rigidity of resin. The surface modified carbon nanotube provided by the invention has important significances and application prospects in aspects of high molecular material development, polymer modification, high performance, multi-functionalization and the like.
Description
Technical field
The present invention relates to a kind of inorganic nano-tube and preparation method thereof, particularly a kind of surface-modified carbon nanotubes and preparation method thereof.
Background technology
Since (Iijima) found carbon nanotube (CNT), the excellent properties of the numerous uniquenesses of CNT was found that constantly people are dense day by day to the interest of CNT research and development from the Japanese electron microscope expert of NEC Corporation Iijima in 1991.The huge Application Areas of CNT is the preparation polymer based nanocomposites.
Research shows, CNT in polymeric matrix good dispersion and with the good interface bonding force of resin be the key of preparation high-performance CNT/ polymer matrix composite.Therefore, the surface-treated of CNT is the important content of CNT research and development.Because fast-developing modern industry is more and more, increasingly high to the requirement of high performance material, therefore, " high performance, multifunction " becomes the target of investigation of materials.Big quantity research shows that CNT is having one's own knack aspect the rigidity that improves thermosetting resin, the thermotolerance, still, improve aspect toughness, the flame retardant resistance but very limited.Therefore, on the basis that keeps the original performance advantage of CNT, how improving its toughness that improves polymkeric substance and flame retardant resistance is to realize the key of CNT to " multi-functional " modified object of polymkeric substance.
In recent years, researchers are received fire retardant on the CNT, to have obtained excellent flame-retardant performance.For example, bibliographical information with the expansion type flame retardant grafting or be coated on the CNT, be used for ABS or polyacrylic fire-retardant; Obtained the excellent research result (referring to 1. Hai-yun Ma, Li-fang Tong, Functionalizing Carbon Nanotubes by Grafting on Intumescent Flame Retardant:Nanocomposite Synthesis; Morphology, Rheology, and Flammability; Advanced Functional Materials; 2008,18,414-421; 2. Ping ' an Song, Lihua Xu, Zhenghong Guo; Yan Zhang and Zhengping Fang; Flame-retardant-wrapped carbon nanotubes for simultaneously improving the flame retardancy and mechanical properties of polypropylene, Journal of Materials Chemistry, 2008; 18,5083 – 5091).Research work has proved that it is an effective way that improves flame retardant resistance that expansion type flame retardant is received CNT.But the last grafts of CNT is IFR, exist poor with the consistency of polymkeric substance, to reduce polymer insulation property etc. main not enough; The existence of a large amount of in addition aromatic nucleus, toughness reinforcing unfavorable to thermosetting resin.
Chinese invention patent (CN 102181074 A) discloses the technical scheme that a kind of preparation has the carbon nanotube of DOPO group; Earlier respectively carbon nanotube and DOPO are had specific chemical group through chemical reaction, make the DOPO that has hydroxyl and the carbon nanotube of chloride; To have the DOPO of hydroxyl and the carbon nanotube of chloride again and react, obtain having the carbon nanotube of DOPO group, can poly limiting oxygen index(LOI) be brought up to 27.Yet treated carbon nanotube does not have active reactive group, makes that the interface performance of carbon nanotube and polymkeric substance is not good, thereby the mechanical property of matrix material is difficult to obtain to ensure.In addition, this technology does not meet the requirement of modern society to the feature of environmental protection carbon nanotube being carried out need use a large amount of poisonous halogen reagent in the chloride process.
Document " preparation of polysiloxane-grafted carbon nanotube and polymer composites and performance " (king's honey; Northeast Forestry University's master thesis; 2010) with polysiloxane-grafted to carbon nanotube; The nanotube (MWNTs-DPD) of graft polysiloxane is joined in the polycarbonate (PC); Compare with the carbon nanotube (MWNTs-COOH) of band carboxyl, though MWCNT-DPD can reduce the burning molten drop, but the limiting oxygen index(LOI) of PC/MWNTs-DPD is reduced to 23～26 from 28 of pure PC.Meanwhile, the straight chain type ZGK 5 does not have abundant active function groups.So the interface adhesion of MWCNT-DPD and polycarbonate is low, therefore the mechanical property of prepared matrix material reduces.
In sum, also do not have a kind of CNT can have the effect of " multiple modified " to polymer materials in the prior art, therefore novel C NT with " multiple modified " function of research and development and preparation method thereof has important use and is worth.Wherein, the modification CNT that " multiple modified " is embodied in preparation has a large amount of active reactive groups, thereby is implemented in the good distribution in the thermosetting resin; Simultaneously modification CNT with molecular structure can keep giving thermosetting resin excellent flame-retardant performance and toughness on resin thermotolerance and the inflexible basis.
Summary of the invention
In order to overcome the deficiency that prior art exists, the object of the present invention is to provide the molecular structure and the performance advantage of a kind of integrated carbon nanotube, hyperbranched polyorganosiloxane and phospho hetero phenanthrene structure, and contain carbon nanotube of reactive group and preparation method thereof.
Realize that the technical scheme that the object of the invention adopted provides a kind of surface-modified carbon nanotubes, carbon nano tube surface is connected to the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene structure and amino with the form of chemical bond.
A kind of method for preparing above-mentioned surface-modified carbon nanotubes comprises the steps:
(1) under anhydrous condition and nitrogen protection, 1:1 in molar ratio will contain the tri-alkoxy siloxanes and 9 of epoxide group, and the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound mixes and forms mixture A; Press mass ratio again, 100 parts mixture A and 1～3 part of catalyzer triphenyl phosphorus are mixed, join in 200 parts the solvent, under agitation condition, be warming up to 95～100 ℃, keep condensing reflux to continue reaction 6～10 hours; After the cooling, remove catalyzer through elimination, solvent seasoning is removed in underpressure distillation, obtains containing the trialkoxy silane of phospho hetero phenanthrene structure and hydroxyl;
(2) be 1:0.1～1:1 in molar ratio, the phospho hetero phenanthrene structure that contains that step (1) makes is mixed with the trialkoxy silane that contains amino with the trialkoxy silane of hydroxyl, form mixture B; Press the mol ratio of element silicon and water, 11～16 parts of zero(ppm) water and 10 parts of mixture B are mixed, under agitation condition, slowly dropwise add 0.001～0.003 part of catalyst B; Be warming up to 50～60 ℃; Continue reaction 4～7 hours, purified, filtration, underpressure distillation obtain transparent liquid; After purified again, filtration, underpressure distillation, the vacuum-drying, promptly obtain a kind of phospho hetero phenanthrene structure and amino hyperbranched poly silane of containing; Described catalyst B is hydrochloric acid, sulfuric acid, tosic acid, TMAH, tetraethyl ammonium hydroxide, sodium hydroxide or Pottasium Hydroxide;
(3) press mass ratio 20:1～30:1, the phospho hetero phenanthrene structure that contains that step (2) makes is mixed supersound process 0.5～2 hour with amino hyperbranched polyorganosiloxane with the epoxide function carbon nano tube; Be under 60～80 ℃ the condition in temperature; Constant temperature stirred 8～12 hours, after reaction finishes, and suction filtration; Washing obtains surface-modified carbon nanotubes.
The described trialkoxy silane that contains epoxy group(ing) is the 3-oily ether oxygen base propyl trimethoxy silicane that shrinks, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, 2-(3,4-epoxy cyclohexane alkyl) ethyl triethoxysilane or their arbitrary combination.
The described trialkoxy silane that contains amino is the 3-TSL 8330, γ-An Bingjisanyiyangjiguiwan, or their combination.
Described epoxide function carbon nano tube is epoxide function single wall or epoxide function multi-walled carbon nano-tube.
Compared with prior art, the beneficial effect that the present invention obtained is following:
1, the prepared modification CNT of the present invention utilizes the characteristics of hyperbranched polyorganosiloxane space multistory globosity; Through a series of reaction; At a large amount of amino active reactive group of carbon nano tube surface grafting; Reach active reactive group " amplification " effect quantitatively, for carbon nanotube obtains good dispersion and consistency provides very favorable condition in resin matrix.The existence of these reactive groups simultaneously also has great application prospect for research and development, polymer modification and the high performance of the further modification of CNT and application, novel high polymer material, aspect such as multiple functionalized.
2, the prepared surface-treated CNT of the present invention; The advantage that has CNT, hyperbranched polyorganosiloxane and phospho hetero phenanthrene compound simultaneously; Make CNT on the basis that keeps its original performance advantage; Can improve the toughness and the flame retardant resistance of polymkeric substance simultaneously, thereby realize the target of CNT " multi-functional " modification of polymkeric substance.
3, aspect fire-retardant, not only kept hyperbranched polyorganosiloxane and phosphonium flame retardant in the advantage that improves aspect the flame retardant resistance, and, obtained the synergistic effect that the two produced more fully, thereby obtained better flame retardant resistance through the two Chemical bond.
4, the outstanding over-all properties, particularly thermotolerance, electrical insulating property, the toughness that have of hyperbranched polyorganosiloxane has been guaranteed the stable on heating maintenance of carbon nanotube, can realize toughness reinforcing to thermosetting resin simultaneously.
5, the preparation method of surface-treated CNT provided by the invention has the advantages that operating procedure is simple, the starting material source is abundant, suitability is wide.
Description of drawings
Fig. 1 is in the embodiment of the invention 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound and the comparison diagram that contains the ir spectra of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane;
Fig. 2 is in the embodiment of the invention 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound with contain phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
1The comparison diagram of H NMR collection of illustrative plates;
Fig. 3 is in the embodiment of the invention 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound with contain phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
31The comparison diagram of P NMR collection of illustrative plates;
Fig. 4 contains phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane in the embodiment of the invention
29The SiNMR collection of illustrative plates;
Fig. 5 is the structural representation of a kind of surface-modified carbon nanotubes of providing of the embodiment of the invention;
Fig. 6 is a kind of surface-modified carbon nanotubes that provides of the embodiment of the invention and the XPS comparison diagram of acidifying carbon nanotube;
Fig. 7 is a kind of surface-modified carbon nanotubes that provides of the embodiment of the invention and the Raman spectrum comparison diagram of epoxidation carbon nanotube.
Embodiment
Below in conjunction with accompanying drawing and embodiment, technical scheme of the present invention is done further to describe.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 23.6g 3-shrink oily ether oxygen base propyl trimethoxy silicane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 0.45g catalyzer triphenyl phosphorus and add the 100g n-propyl alcohol, be warming up to 95 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and solvent is removed in underpressure distillation, and filters and remove catalyzer, carries out vacuum-drying, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.Its infrared comparison diagram is Fig. 1.
After getting above-mentioned all trialkoxy silane, 1.8g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, add 4mol/L hydrochloric acid 2.5mL and also be heated to 50 ℃ of sustained reactions 4 hours, underpressure distillation obtains crude product; After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.Its
1H NMR,
31P NMR with
29The SiNMR collection of illustrative plates is respectively referring to accompanying drawing 2,3 and 4.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 2 hours; Be that constant temperature stirred 12 hours under 80 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.Its structural representation is shown in accompanying drawing 5.Its XPS and Raman spectrum are respectively referring to accompanying drawing 6 and 7.
Referring to accompanying drawing 1; It is 9 in the present embodiment; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and the infrared spectrum contrast that contains phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane; As can be seen from Figure 1 some: (1) 9,10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound is at 2438cm
-1The absorption peak of the P-H key at place is stronger; And this peak does not occur in containing the infrared figure of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane; Showing 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound is introduced in the hyperbranched polyorganosiloxane through the reaction with epoxide group.(2) 738.71cm
-1, 1242.32cm
-1And 1482.13cm
-1Represent P-O-Ph respectively, the charateristic avsorption band of P=O and P-Ph has proved that institute's synthetic product contains the phospho hetero phenanthrene structure.(3) 1098.43 cm
-1Represent the charateristic avsorption band of Si-O-Si, proved in institute's synthetic product and contained the Si-O-Si structure.
Referring to accompanying drawing 2, it is in the present embodiment 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound with contain phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
1H NMR collection of illustrative plates.Can see; The spectrogram that contains the amino hyperbranched polyorganosiloxane of phospho hetero phenanthrene structure does not occur 9; The 10-dihydro-9-oxy is assorted-peak of Wasserstoffatoms on the P-H key that the 10-phospho hetero phenanthrene-10-oxide compound spectrogram is shown; Showing 9 once more, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound has been introduced in through the reaction with epoxide group and contained in phospho hetero phenanthrene structure and the amino hyperbranched polyorganosiloxane.
Referring to accompanying drawing 3, it is 9 in the present embodiment, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound with contain phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
31P NMR collection of illustrative plates.Comparing result shows; 15.62ppm be 9, the 10-dihydro-9-oxy is assorted-peak of the phosphorus atom of 10-phospho hetero phenanthrene-10-oxide compound, 11.16ppm and 26.46ppm are the peak that contains phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane phosphorus atom; Both peaks are different; Show 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound with the epoxide group reaction, the phospho hetero phenanthrene structure successfully has been incorporated into to be contained in phospho hetero phenanthrene structure and the amino hyperbranched polyorganosiloxane.
Referring to accompanying drawing 4, it is to contain phospho hetero phenanthrene structure and epoxy group(ing) hyperbranched polyorganosiloxane in the present embodiment
29Si NMR collection of illustrative plates.Can find out that three chemical shifts have appearred respectively in-64.34 ppm ,-59.23 ppm and-48.36 ppm places, they represent the branching chain link of siloxanes, linear chain link and end-blocking chain link respectively, have proved that polymkeric substance is a hyperbranched polyorganosiloxane.The degree of branching of utilizing formula to calculate to contain phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane is 0.69.
Comprehensive accompanying drawing 1～4 can learn, by present embodiment step 1 synthetic product for containing phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane.
Referring to accompanying drawing 5, it is the structural representation of the surface-modified carbon nanotubes that provides of technical scheme of the present invention.Carbon nano tube surface is connected to the form of chemical bond and contains phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane.
Referring to accompanying drawing 6, it is the surface-modified carbon nanotubes that provides of present embodiment and the XPS comparison diagram of carboxylic carbon nano-tube; Can know by the figure result, can find out N from the ownership of bound energy
1s, P
2pWith Si
2pBound energy be respectively at 397.1eV, 133.7eV and 102.2eV, show the existence that nitrogen element, phosphoric and element silicon are arranged in the carbon nanotube, explain in the surface-modified carbon nanotubes successfully to introduce to contain phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane.
Referring to accompanying drawing 7, it is the surface-modified carbon nanotubes that provides of present embodiment and the Raman spectrum comparison diagram of non-modified carbon nanotube; Through comparing the strength ratio that characterizes G peak (representing crystal carbon) and D peak (representative amorphous carbon) on the Raman spectrum, I
G/ I
DValue more little, represent the functionalization degree of polymkeric substance of carbon nano tube surface high more, so this is the strong evidence of surface modification of carbon nanotube.Can know the I of carbon nanotube and surface-modified carbon nanotubes by Fig. 7 result
G/ I
DBe respectively 0.57 and 0.41, proved effectively to contain the phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane is grafted on the carbon nanotube.
Referring to table 1, it is the ultimate analysis EDS table of the surface-modified carbon nanotubes that makes of present embodiment and non-modified carbon nanotube.
Table 1 non-modified carbon nanotube and embodiment one surface-modified carbon nanotubes EDS data
| ? | C content (wt%) | O content (wt%) | Si content (wt%) | N content (wt%) | P content (wt%) |
| Unmodified multi-walled carbon nano-tubes | 99.18 | 0.82 | 0 | 0 | 0 |
| The surface-modified carbon nanotubes that present embodiment provides | 88.24 | 7.18 | 3.17 | 0.54 | 0.87 |
Can see by table 1; Compare with the composition of the multi-walled carbon nano-tubes of non-modified; Contain nitrogen element, phosphoric and element silicon in the surface-modified carbon nanotubes that present embodiment makes; Simultaneously oxygen element content raises, and explains to contain the phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane has successfully been introduced carbon nanotube.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.6g 2-(3; 4-epoxy cyclohexane base) ethyl trimethoxy silane and 21.6g 9; The 10-dihydro-9-oxy is assorted-and after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes, add 1.4g catalyzer triphenyl phosphorus and add 100g methyl alcohol, be warming up to 100 ℃ and keep condensing refluxes to continue reaction 10 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 2.2g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, add 4mol/L hydrochloric acid 7.5mL and also be heated to 60 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function SWCN is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 2 hours; Be that constant temperature stirred 12 hours under 80 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.6g 2-(3; 4-epoxy cyclohexane alkyl) ethyl trimethoxy silane and 21.6g 9; The 10-dihydro-9-oxy is assorted-and after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes, add 1.3g catalyzer triphenyl phosphorus and add 100g ethanol, be warming up to 97 ℃ and keep condensing refluxes to continue reaction 8 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 17.9g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L hydrochloric acid 7.5mL and be heated to 55 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.3 hours; Be that constant temperature stirred 10 hours under 76 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
Take by weighing surface-modified carbon nanotubes and 100g bisphenol A cyanate ester that the 0.35g above-mentioned steps obtains, they are mixed 15min under 80 ℃ temperature condition, promptly obtain a kind of modified cyanic acid ester resin.Pouring the modified cyanic acid ester resin that obtains into preheating pours in the mould; In 150 ℃ of vacuum defoamations 1 hour; Be cured and aftertreatment according to the technology of 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h respectively again; The demoulding behind the naturally cooling promptly obtains solidified surface-modified carbon nanotubes/cyanate composite material.Its typical performance is listed in the table 2.
The preparation of comparative example 1: the 100g bisphenol A cyanate ester is stirred 15min under 80 ℃ of conditions; Pouring the liquid cyanate that obtains into preheating pours in the mould; In 150 ℃ of vacuum defoamations 1 hour; Be cured and aftertreatment according to the technology of 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h respectively, the demoulding behind the naturally cooling promptly obtains the solidified cyanate ester resin again.Its typical performance is listed in the table 2.
The preparation of comparative example 2: pure multi-walled carbon nano-tubes of 0.35g and 100g bisphenol A cyanate ester are mixed 15min under 80 ℃, promptly obtain a kind of cyanate composite material.Pouring the modified cyanic acid ester resin that obtains into preheating pours in the mould; In 150 ℃ of vacuum defoamations 1 hour; Be cured and aftertreatment according to the technology of 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h respectively again; The demoulding behind the naturally cooling promptly obtains solidified carbon nanotube/cyanate composite material.Its typical performance is listed in the table 2.
Referring to subordinate list 2, it is the surface-modified carbon nanotubes/cyanate composite material of present embodiment preparation, the cyanate cured resin of comparative example 1 preparation and the typical performance of carbon nanotube/cyanate composite material that comparative example 2 prepares.Contrast two comparative examples, can find out, original carbon nanotube is to cyanate ester resin comprehensively modifying DeGrain, and significantly reduced the second-order transition temperature of cyanate ester resin.And second-order transition temperature, limiting oxygen index(LOI), impact and the flexural strength of the surface-modified carbon nanotubes/cyanate composite material of embodiment 3 preparations all are significantly higher than the corresponding data of two comparative examples; Show that surface-modified carbon nanotubes that the present invention prepares can significantly improve the thermotolerance of cyanate ester resin, fire-retardant, toughness and intensity, i.e. the surface-modified carbon nanotubes of the present invention preparation has great application prospect aspect modified resin.
Table 2
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 100 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 17.9g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 4mol/L sulfuric acid 4.4mL also was heated to 56 ℃ of sustained reactions 7 hours, and underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.3 hours; Be that constant temperature stirred 10 hours under 76 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 100 ℃ and keep condensing reflux to continue reaction 9 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 2.99g γ-An Bingjisanyiyangjiguiwan and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L tosic acid 3.5mL and be heated to 57 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
2g epoxide function multi-walled carbon nano-tube, 3g epoxide function SWCN are contained the phospho hetero phenanthrene structure with 100g and mix with amino hyperbranched polyorganosiloxane; Supersound process 1.3 hours; Be under 76 ℃ the condition in temperature; Constant temperature stirred 10 hours, and reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 98 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 17.9g γ-An Bingjisanyiyangjiguiwan and 2.5g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L TMAH 4.0mL and be heated to 60 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function SWCN is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.2 hours; Be that constant temperature stirred 9 hours under 70 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
1, contains the synthetic of phospho hetero phenanthrene structure and ammonia hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 97 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
Get above-mentioned all contain trialkoxy silane, the 3.9g 3-TSL 8330 of phospho hetero phenanthrene structure and hydroxyl; After 4.0g γ-An Bingjisanyiyangjiguiwan and 2.2g zero(ppm) water mix; Add 4mol/L sulfuric acid 4.5mL and be heated to 60 ℃ of sustained reactions 6 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.8 hours; Be that constant temperature stirred 10 hours under 71 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 100 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 17.9g 3-TSL 8330 and 2.7g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L sulfuric acid 4.1 mL and be heated to 54 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.1 hours; Be that constant temperature stirred 10 hours under 78 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 96 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 14.9g 3-TSL 8330 and 2.8g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L Pottasium Hydroxide 4.4mL and be heated to 54 ℃ of sustained reactions 6 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.7 hours; Be that constant temperature stirred 11 hours under 78 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 96 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 12.9g 3-TSL 8330 and 2.5g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L sulfuric acid 4.4mL and be heated to 53 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.0 hours; Be that constant temperature stirred 10 hours under 70 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
Embodiment 11
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 98 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 17.9g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L sulfuric acid 4.4mL and be heated to 53 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.9 hours; Be that constant temperature stirred 10 hours under 72 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
Embodiment 12
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane.
Under anhydrous and nitrogen protection condition; With 24.8g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; The mixed solution that adds 1.4g catalyzer triphenyl phosphorus adding 100g propyl carbinol and n-propyl alcohol is warming up to 99 ℃ and keeps condensing refluxes to continue reaction 7 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 11.9g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L sulfuric acid 4.2mL and be heated to 52 ℃ of sustained reactions 4 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function SWCN is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.4 hours; Be that constant temperature stirred 10 hours under 70 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
Embodiment 13
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 28.85g 2-(3; 4-epoxy cyclohexane alkyl) ethyl triethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-and after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes, add 1.3g catalyzer triphenyl phosphorus and add the 100g n-propyl alcohol, be warming up to 98 ℃ and keep condensing refluxes to continue reaction 9 o'clock; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 13.1g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L sodium hydroxide 4.4mL and be heated to 60 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.3 hours; Be that constant temperature stirred 10 hours under 70 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
Embodiment 14
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 12.3g 2-(3,4-epoxy cyclohexane alkyl) ethyl trimethoxy silane, 14.85g 2-(3; 4-epoxy cyclohexane alkyl) ethyl triethoxysilane and 21.6g 9; The 10-dihydro-9-oxy is assorted-and after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes, add 1.3g catalyzer triphenyl phosphorus and add the 100g n-propyl alcohol, be warming up to 98 ℃ and keep condensing refluxes to continue reaction 9 o'clock; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 13.5g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L tetraethyl ammonium hydroxide 3.5mL and be heated to 56 ℃ of sustained reactions 8 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.5 hours; Be that constant temperature stirred 10 hours under 70 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 12.4g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane; 14.85g 2-(3,4-epoxy cyclohexane alkyl) ethyl triethoxysilane and 21.6g 9, the 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 98 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 17.9g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L tetraethyl ammonium hydroxide 3.4mL and be heated to 52 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.9 hours; Be that constant temperature stirred 10 hours under 71 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
Embodiment 16
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition; With 12.4g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane; 12.3g 2-(3,4-epoxy cyclohexane alkyl) ethyl trimethoxy silane and 21.6g 9, the 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 98 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 17.9g 3-TSL 8330 and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L tetraethyl ammonium hydroxide 3.3mL and be heated to 51 ℃ of sustained reactions 7 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.9 hours; Be that constant temperature stirred 10 hours under 72 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
Embodiment 17
1, contains the synthetic of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane
Under anhydrous and nitrogen protection condition, with 9.92g 3-glycidyl ether oxygen base propyl group methyldiethoxysilane, 7.38g 2-(3; 4-epoxy cyclohexane alkyl) ethyl trimethoxy silane; 8.65g 2-(3,4-epoxy cyclohexane alkyl) ethyl triethoxysilane and 21.6g 9, the 10-dihydro-9-oxy is assorted-after the 10-phospho hetero phenanthrene-the 10-oxide compound mixes; Add 1.4g catalyzer triphenyl phosphorus and add the 100g propyl carbinol, be warming up to 96 ℃ and keep condensing reflux to continue reaction 6 hours; Question response finishes, and carries out vacuum-drying, and solvent is removed in underpressure distillation, and filters and remove catalyzer, obtains the transparent trialkoxy silane that contains phospho hetero phenanthrene structure and hydroxyl.
After getting above-mentioned all trialkoxy silane, 14.9g 3-TSL 8330 and 2.8g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing; Add 4mol/L tetraethyl ammonium hydroxide 3.4mL and be heated to 51 ℃ of sustained reactions 6 hours, underpressure distillation obtains crude product;
After crude product purifying, filtration, underpressure distillation and vacuum-drying, promptly get a kind of phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane of containing.
2, the preparation of surface-modified carbon nanotubes
5g epoxide function multi-walled carbon nano-tube is contained the phospho hetero phenanthrene structure with 100g to be mixed with amino hyperbranched polyorganosiloxane; Supersound process 1.4 hours; Be that constant temperature stirred 10 hours under 70 ℃ the condition in temperature, reaction finishes the after scouring filtering drying and obtains surface-modified carbon nanotubes.
Claims (5)
1. surface-modified carbon nanotubes is characterized in that: described carbon nano tube surface is connected to the form of chemical bond and contains phospho hetero phenanthrene structure and amino hyperbranched polyorganosiloxane.
2. a method for preparing surface-modified carbon nanotubes as claimed in claim 1 is characterized in that comprising the steps:
(1) under anhydrous condition and nitrogen protection, 1:1 in molar ratio will contain the tri-alkoxy siloxanes and 9 of epoxide group, and the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound mixes and forms mixture A; Press mass ratio again, 100 parts mixture A and 1～3 part of catalyzer triphenyl phosphorus are mixed, join in 200 parts the solvent, under agitation condition, be warming up to 95～100 ℃, keep condensing reflux to continue reaction 6～10 hours; After the cooling, remove catalyzer through elimination, solvent seasoning is removed in underpressure distillation, obtains containing the trialkoxy silane of phospho hetero phenanthrene structure and hydroxyl;
(2) be 1:0.1～1:1 in molar ratio, the phospho hetero phenanthrene structure that contains that step (1) makes is mixed with the trialkoxy silane that contains amino with the trialkoxy silane of hydroxyl, form mixture B; Press the mol ratio of element silicon and water, 11～16 parts of zero(ppm) water and 10 parts of mixture B are mixed, under agitation condition, slowly dropwise add 0.001～0.003 part of catalyst B; Be warming up to 50～60 ℃; Continue reaction 4～7 hours, purified, filtration, underpressure distillation obtain transparent liquid; After purified again, filtration, underpressure distillation, the vacuum-drying, promptly obtain a kind of phospho hetero phenanthrene structure and amino hyperbranched poly silane of containing; Described catalyst B is hydrochloric acid, sulfuric acid, tosic acid, TMAH, tetraethyl ammonium hydroxide, sodium hydroxide or Pottasium Hydroxide;
(3) press mass ratio 20:1～30:1, the phospho hetero phenanthrene structure that contains that step (2) makes is mixed supersound process 0.5～2 hour with amino hyperbranched polyorganosiloxane with the epoxide function carbon nano tube; Be under 60～80 ℃ the condition in temperature; Constant temperature stirred 8～12 hours, after reaction finishes, and suction filtration; Washing obtains surface-modified carbon nanotubes.
3. the preparation method of a kind of surface-modified carbon nanotubes according to claim 2; It is characterized in that: the described trialkoxy silane that contains epoxy group(ing) is the 3-oily ether oxygen base propyl trimethoxy silicane that shrinks; 2-(3; 4-epoxy cyclohexane base) ethyl trimethoxy silane, 2-(3,4-epoxy cyclohexane alkyl) ethyl triethoxysilane or their arbitrary combination.
4. the preparation method of a kind of surface-modified carbon nanotubes according to claim 2 is characterized in that: described to contain amino trialkoxy silane be the 3-TSL 8330, γ-An Bingjisanyiyangjiguiwan, or their arbitrary combination.
5. the preparation method of a kind of surface-modified carbon nanotubes according to claim 2, it is characterized in that: described epoxide function carbon nano tube is epoxide function single wall or epoxide function multi-walled carbon nano-tube.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980736A (en) * | 2014-04-13 | 2014-08-13 | 北京化工大学 | Phosphaphenanthrene compound 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) grafted and modified sepiolite fibers and preparation method thereof |
| CN104861165A (en) * | 2015-06-03 | 2015-08-26 | 宁波工程学院 | Preparation method of mercapto-alkene polymer flame-retardant system |
| CN109775689A (en) * | 2018-12-12 | 2019-05-21 | 深圳烯湾科技有限公司 | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application |
| CN110218327A (en) * | 2019-05-31 | 2019-09-10 | 福建师范大学 | Hyperbranched phosphorous poly- silicon oxygen borine fire retardant of one kind and preparation method thereof |
| US10633531B2 (en) | 2016-10-14 | 2020-04-28 | International Business Machines Corporation | Functionalized carbon nanotubes |
| CN112267306A (en) * | 2020-10-18 | 2021-01-26 | 李东靖 | Flame-retardant anti-static fabric and preparation method thereof |
| CN115819776A (en) * | 2023-02-22 | 2023-03-21 | 山东东岳有机硅材料股份有限公司 | Self-repairing polysiloxane elastomer based on strong and weak hydrogen bond effects and preparation method thereof |
| CN116218119A (en) * | 2023-03-03 | 2023-06-06 | 广东热浪新材料科技有限公司 | Flame-retardant solid surface material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486927A (en) * | 2003-07-31 | 2004-04-07 | 上海交通大学 | Super-branched polymer grafted carbon nanotube and its prepn process |
| CN102199294A (en) * | 2011-04-12 | 2011-09-28 | 苏州大学 | Hyperbranched polysiloxane and preparation method thereof |
-
2012
- 2012-01-31 CN CN 201210021680 patent/CN102585291B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486927A (en) * | 2003-07-31 | 2004-04-07 | 上海交通大学 | Super-branched polymer grafted carbon nanotube and its prepn process |
| CN102199294A (en) * | 2011-04-12 | 2011-09-28 | 苏州大学 | Hyperbranched polysiloxane and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| 《Materials Chemistry》 20110328 Dongxian Zhuo, et al. "Flame retardancy materials based on a novel fully end-capped hyperbranched polysiloxane and bismaleimide/diallylbisphenol A resin with simultaneously improved integrated performance" 第6584－6585页 1 , * |
| 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 20100415 王蜜 "聚硅氧烷接枝碳纳米管及聚合物复合材料的制备与性能" 第16页倒数第1-3行，第17页第1-3行 1 , * |
| 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 20091215 仲含芳 "含磷聚硅氧烷的合成及其在PC/ABS中的应用" 第35-39页 1 , * |
| DONGXIAN ZHUO, ET AL.: ""Flame retardancy materials based on a novel fully end-capped hyperbranched polysiloxane and bismaleimide/diallylbisphenol A resin with simultaneously improved integrated performance"", 《MATERIALS CHEMISTRY》, 28 March 2011 (2011-03-28), pages 6584 - 6585 * |
| 仲含芳: ""含磷聚硅氧烷的合成及其在PC/ABS中的应用"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, 15 December 2009 (2009-12-15), pages 35 - 39 * |
| 王蜜: ""聚硅氧烷接枝碳纳米管及聚合物复合材料的制备与性能"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 April 2010 (2010-04-15) * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980736A (en) * | 2014-04-13 | 2014-08-13 | 北京化工大学 | Phosphaphenanthrene compound 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) grafted and modified sepiolite fibers and preparation method thereof |
| CN104861165A (en) * | 2015-06-03 | 2015-08-26 | 宁波工程学院 | Preparation method of mercapto-alkene polymer flame-retardant system |
| US10633531B2 (en) | 2016-10-14 | 2020-04-28 | International Business Machines Corporation | Functionalized carbon nanotubes |
| CN109775689A (en) * | 2018-12-12 | 2019-05-21 | 深圳烯湾科技有限公司 | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application |
| CN110218327A (en) * | 2019-05-31 | 2019-09-10 | 福建师范大学 | Hyperbranched phosphorous poly- silicon oxygen borine fire retardant of one kind and preparation method thereof |
| CN110218327B (en) * | 2019-05-31 | 2021-03-16 | 福建师范大学 | Hyperbranched phosphorus-containing polysiloxane borane flame retardant and preparation method thereof |
| CN112267306A (en) * | 2020-10-18 | 2021-01-26 | 李东靖 | Flame-retardant anti-static fabric and preparation method thereof |
| CN115819776A (en) * | 2023-02-22 | 2023-03-21 | 山东东岳有机硅材料股份有限公司 | Self-repairing polysiloxane elastomer based on strong and weak hydrogen bond effects and preparation method thereof |
| CN116218119A (en) * | 2023-03-03 | 2023-06-06 | 广东热浪新材料科技有限公司 | Flame-retardant solid surface material and preparation method thereof |
| CN116218119B (en) * | 2023-03-03 | 2023-09-22 | 广东热浪新材料科技有限公司 | Flame-retardant solid surface material and preparation method thereof |
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