CN102604383A - Carbon nano tube/thermosetting resin composite material and preparation method thereof - Google Patents
Carbon nano tube/thermosetting resin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon nano tube/thermosetting resin composite material and a preparation method of the carbon nano tube/thermosetting resin composite material. According to weight, 100 parts of thermosetting resin and 0.25-4 parts of surface modified carbon nano tube are mixed uniformly at a resin melting temperature, so that the carbon nano tube/thermosetting resin composite material is obtained. The surface modified carbon nano tube is as follows: hyperbranched polysiloxane containing a phosphenanthrene structure and an amino is connected on the surface of the surface modified carbon nano tube in a chemical bond manner. Based on the heat resistance of original bismaleimide resin, the prepared composite material has high toughness, high strength, low curing temperature and good flame retardance, and can be taken as a high-performance resin matrix, an adhesive, an insulated paint and the like to be widely applied to such high-tech fields as aerospace, electric products, transportation and the like. The preparation method of the composite material, provided by the invention, has the advantages of wide applicability, good environmental protection, simplicity in operation process and the like.
Description
Technical field
The present invention relates to technical field of polymer composite materials, be specifically related to a kind of carbon nanotube/thermoset ting resin composite and preparation method thereof.
Background technology
Since the nineteen nineties Japan's electron microscope expert of NEC Corporation Iijima (Iijima) was found carbon nanotube (CNT), the CNT/ thermoset ting resin composite just became the research and development focus of field of materials.Compare with thermosetting resin, the CNT/ thermoset ting resin composite generally has high intensity, modulus and flame resistivity; But the two is not having marked difference aspect toughness and the flame retardant resistance, can not satisfy the requirement of modern industry to high performance material.Therefore, CNT is carried out modification, enable to give the key that the good toughness of matrix material, flame retardant resistance become preparation high-performance CNT/ thermoset ting resin composite.
In order to obtain flame retardant resistance, people receive fire retardant on the CNT.Bibliographical information with the expansion type flame retardant grafting or be coated on the CNT, be used for ABS or polyacrylic fire-retardant, obtained good result (referring to document: 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).Its research work has proved that it is an effective way that improves flame retardant resistance that expansion type flame retardant is received CNT.But, be grafted to the expansion type flame retardant on the CNT, exist a lot of not enough, as poor with the consistency of polymkeric substance, reduce polymer insulation property etc.; Meanwhile, have a large amount of aromatic nucleus in this expansion type flame retardant, this is toughness reinforcing very unfavorable to thermosetting resin obviously.
Chinese invention patent (CN 102181074 A) discloses and a kind of carbon nanotube and DOPO has been 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 reacts; Obtain having the technology of the carbon nanotube of DOPO group, it can bring up to 27 with poly limiting oxygen index(LOI).But treated carbon nanotube does not have active reactive group, makes that the interface performance of carbon nanotube and polymkeric substance is very poor, thereby matrix material is difficult to obtain excellent mechanical property.In addition, this invention does not obviously meet the requirement of modern society to the feature of environmental protection in a large amount of poisonous halogen reagent of carbon nanotube being carried out need use 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.In addition, 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, modification CNT of the prior art flame retardant resistance, toughness is not reached and the interface adhesion of resin combines, and therefore the performance of prepared CNT/ thermoset ting resin composite can not obtain comprehensive raising.
Publication number is in the Chinese invention patent of CN102219906A, CN102199294A, CN102276836A and CN102250350A; The hyperbranched polyorganosiloxane of serial phospho hetero phenanthrene structure and reactive group and the technical scheme of modified heat convertible resin thereof are provided; Confirmed that these hyperbranched polyorganosiloxanes can keep having possessed H.T. and good flame retardant resistance on the original outstanding stable on heating basis of cyanate and bimaleimide resin.Yet these hyperbranched polyorganosiloxanes that contain phospho hetero phenanthrene structure and reactive group contain more silicon hydroxyl, its in depositing process further dehydrating condensation form the Si-O-Si structure, cause crosslinked (reference: Petar R. Dvornic; Vesna V. Gerov, Milutin N. Govedarica, Polymerization by Hydrosilation. 2. Preparation and Characterization of High Molecular Weight Poly [(1; 1,3,3-tetramethyldisiloxanyl) ethylene] from 1; 3-Dihydridotetramethyldisiloxane and 1; 3-Divinyltetramethyldisiloxane, Macromolecules, 1994; 27 (26), pp 7575 – 7580).Therefore, the hyperbranched polyorganosiloxane that provides has working life, after surpassing working life, re-use just to cause preparation technology's property of modified resin poor, and the poor performance of prepared modified resin.
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 modified carbon nano-tube/thermoset ting resin composite of reactive group and preparation method thereof.
Realize that the technical scheme that the object of the invention adopted provides a kind of carbon nanotube/thermoset ting resin composite, by weight, it comprises 100 parts of thermosetting resins and 0.2～4 part of surface-modified carbon nanotubes; Described surface-modified carbon nanotubes is the form grafted modified ultra-branching ZGK 5 of carbon nano tube surface with chemical bond, and its percentage of grafting is 15.0wt%～20.0wt%; Described surface-treated hyperbranched polyorganosiloxane contains the hyperbranched polyorganosiloxane of phospho hetero phenanthrene structure and amido for the surface.
Described thermosetting resin is cyanate ester resin, bimaleimide resin, epoxy resin, or their arbitrary combination.
Technical scheme of the present invention also comprises a kind of preparation method of carbon nanotube/thermoset ting resin composite, 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 of amino-contained 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 surface-treated hyperbranched poly silane that contains phospho hetero phenanthrene structure and amido; 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 surface-treated hyperbranched polyorganosiloxane that step (2) is made mixes with the epoxide function carbon nano tube, supersound process 0.5～2 hour; 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;
(4) by weight, the surface-modified carbon nanotubes that 100 parts of thermosetting resins and 0.25～4 part of step (3) are obtained mixes under thermosetting resin fused temperature, obtains a kind of carbon nanotube/thermoset ting resin composite.
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 trialkoxy silane of described amino-contained is a 3-aminocarbonyl propyl Trimethoxy silane, γ-amine propyl-triethoxysilicane, or their arbitrary 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:
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 amido 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 provides new 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; Inherited the advantage of CNT, hyperbranched polyorganosiloxane and phospho hetero phenanthrene compound simultaneously; Make CNT on the basis that keeps the original performance advantage of CNT; Can improve the toughness and the flame retardant resistance of polymkeric substance simultaneously, thereby realize the target of preparation high-performance CNT/ thermoset ting resin composite.
3, aspect fire-retardant, not only inherited CNT, hyperbranched polyorganosiloxane and phosphonium flame retardant in the advantage that improves aspect the flame retardant resistance, and the Chemical bond through the three, fully guarantee to obtain the synergistic effect that the three produces, thereby obtain better flame retardant resistance.
4, the surface-modified carbon nanotubes of the present invention's preparation; Its surface is connected to the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene structure and amido with the form of chemical bond, institute's grafted hyperbranched polyorganosiloxane, and its reactive group that contains is present in the CNT surface; When the condensation reaction of silicon hydroxyl takes place; Just link together the hyperbranched polyorganosiloxane chain on the different grafting sites, the active amine above it still plays a role, and the Si-O-Si structure of generation still is a soft segment; Overcome the hyperbranched polyorganosiloxane that independent use contains the silicon hydroxyl, had the defective of working life when dehydrating condensation forms the Si-O-Si structure in depositing process.
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 infared spectrum comparison diagram that contains the hyperbranched polyorganosiloxane of phospho hetero phenanthrene structure and amido;
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 superbranching ZGK 5
1H NMR collection of illustrative plates comparison diagram;
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 superbranching ZGK 5
31P NMR collection of illustrative plates comparison diagram;
Fig. 4 contains phospho hetero phenanthrene structure and amino superbranching ZGK 5 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;
Fig. 8 is the DSC curve comparison diagram of the bisphenol A cyanate ester that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples;
Fig. 9 is the TG curve comparison diagram of the bisphenol A cyanate ester that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples;
Figure 10 is the limited oxygen index column comparison diagram of the bisphenol A cyanate ester resin that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples;
Figure 11 is the shock strength column comparison diagram of the bisphenol A cyanate ester resin that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples;
Figure 12 is the flexural strength column comparison diagram of the bisphenol A cyanate ester resin that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples.
Embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is done further to describe.
1, hyperbranched polyorganosiloxane synthetic that contains phospho hetero phenanthrene structure and amido
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, and its infared spectrum is referring to accompanying drawing 1.
After getting above-mentioned all trialkoxy silane, 1.8g 3-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene structure and amido, percentage of grafting is 15.0wt%, its
1H NMR,
31P NMR with
29The SiNMR collection of illustrative plates is 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 the amino superbranching ZGK 5; 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 seen accompanying drawing 6 and 7 respectively.
3, the preparation of carbon nanotube/cyanate (CE) matrix material
Take by weighing surface-modified carbon nanotubes and 100g bisphenol A cyanate ester that 0.25g step 2 obtains, they are mixed under 80 ℃ temperature condition, promptly obtain a kind of carbon nanotube/cyanate composite material.
Referring to accompanying drawing 1, it is 9 in the present embodiment, the 10-dihydro-9-oxy is assorted-and the comparison diagram of 10-phospho hetero phenanthrene-10-oxide compound and the infrared spectrum of the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene structure and amido.By Fig. 1 can find out following 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 the infrared figure that contains phospho hetero phenanthrene structure and amino superbranching ZGK 5; 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 superbranching ZGK 5
1The comparison diagram of H NMR collection of illustrative plates.Visible by Fig. 2; The spectrogram that contains phospho hetero phenanthrene structure amino superbranching ZGK 5 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 superbranching ZGK 5.
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 superbranching ZGK 5
31The comparison diagram of P NMR collection of illustrative plates.Comparing result by Fig. 3 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 superbranching ZGK 5 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 superbranching ZGK 5.
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.Utilizing formula to calculate to contain the degree of branching of phospho hetero phenanthrene structure and amino superbranching ZGK 5 is 0.69.
Comprehensive accompanying drawing 1～4 can be learnt, be the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene structure and amido by present embodiment step 1 synthetic product.
Referring to accompanying drawing 5, it is the structural representation of surface-modified carbon nanotubes.Fig. 5 shows that carbon nano tube surface is connected to the hyperbranched polyorganosiloxane that contains phospho hetero phenanthrene structure and amido with the form of chemical bond.
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 Fig. 6 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 superbranching ZGK 5.
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 superbranching is polysiloxane-grafted to 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
| ? | 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 |
| Surface-modified carbon nanotubes | 88.24 | 7.18 | 3.17 | 0.54 | 0.87 |
EDS data by in the table 1 can be seen; 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 the amino superbranching ZGK 5 has successfully been introduced carbon nanotube.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 20.0wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/cyanate composite material
Under agitation condition, 4g surface-modified carbon nanotubes and 100g bisphenol A cyanate ester are mixed under 130 ℃, promptly obtain a kind of carbon nanotube/cyanate composite material.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 16.2wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/cyanate composite material
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.Pour the modified cyanic acid ester resin that obtains into preheating and pour in the mould, in 150 ℃ of vacuum defoamations 1 hour, more respectively according to 180
0C/2h+200
0C/2h+220
0C/2h and 240
0The technology of C/4h is cured and aftertreatment, and 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 typical performance of cured resin is respectively referring to accompanying drawing 8,9,10,11 and 12.
Method by embodiment 3 prepares surface-modified carbon nanotubes.
Under agitation condition, 0.8g surface-modified carbon nanotubes and 100g bisphenol A cyanate ester are mixed under 110 ℃, promptly obtain carbon nanotube/cyanate composite material.
Pour the carbon nanotube/cyanate composite material that obtains into preheating and pour in the mould, in 150 ℃ of vacuum defoamations 1 hour, more respectively according to 180
0C/2h+200
0C/2h+220
0C/2h and 240
0The technology of C/4h is cured and aftertreatment, and the demoulding behind the naturally cooling promptly obtains solidified carbon nanotube/cyanate composite material.The typical performance of cured resin is respectively referring to accompanying drawing 8,9,10,11 and 12.
Method by embodiment 3 prepares surface-modified carbon nanotubes.
Under agitation condition, 1.3 g surface-modified carbon nanotubes and 100g bisphenol A cyanate ester are mixed under 110 ℃, promptly obtain carbon nanotube/cyanate composite material.
Pour the carbon nanotube/cyanate composite material that obtains into preheating and pour in the mould, in 150 ℃ of vacuum defoamations 2 hours, more respectively according to 180
oC/2h+200
oC/2h+220
oC/2h and 240
oThe technology of C/4h is cured and aftertreatment, and the demoulding behind the naturally cooling promptly obtains solidified carbon nanotube/cyanate composite material.The typical performance of cured resin is respectively referring to accompanying drawing 8,9,10,11 and 12.
Comparative Examples: take by weighing the 50g bisphenol A cyanate ester; After 150 ℃ of fusions, pour in the mould; In 110 ℃ of vacuum defoamations 2 hours; According to program Solidification and the aftertreatment of 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, the demoulding behind the naturally cooling promptly obtains the solidified bisphenol A cyanate ester resin again.The typical performance of cured resin is respectively referring to accompanying drawing 8,9,10,11 and 12.
Referring to accompanying drawing 8, it is the DSC curve comparison diagram of the bisphenol A cyanate ester that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples.As can be seen from Figure 8, compare with bisphenol A cyanate ester, the curing reaction exothermic peak integral body of carbon nanotube/cyanate composite material obviously moves to the low temperature direction, explains that the solidification value of the curing reaction of carbon nanotube/cyanate composite material significantly reduces.
Referring to accompanying drawing 9, it is the TG curve of the bisphenol A cyanate ester that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples, and the representative data of thermal weight loss is referring to table 2 under nitrogen atmosphere.Find that through contrast the initial heat decomposition temperature of carbon nanotube/cyanate composite material all is higher than the cyanate ester resin of non-modified, in addition, carbon nanotube/cyanate composite material is 800
oCarbon yield under the C slightly is superior to the analog value of the bisphenol A cyanate ester that Comparative Examples provides, and has proved that carbon nanotube/cyanate composite material has improved the outstanding thermostability of cyanate ester resin.
Table 2
| ? | | Embodiment | 3 | |
|
| Initial heat decomposition temperature (℃) | 325.8 | 392.9 | 405.9 | 429.8 | |
| 800 ℃ of following carbon yields (wt%) | 33.8 | 36.1 | 37.0 | 38.3 |
Referring to accompanying drawing 10, it is the limited oxygen index column comparison diagram of the bisphenol A cyanate ester resin that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples.Result by Figure 10 shows that the limiting oxygen index(LOI) of carbon nanotube/cyanate composite material is significantly higher than the analog value of unmodified resin, shows that the flame retardant properties of carbon nanotube/cyanate composite material has obtained effective improvement.
Referring to accompanying drawing 11, it is the shock strength column comparison diagram of the bisphenol A cyanate ester resin that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples.Result by Figure 11 shows that the shock strength of carbon nanotube/cyanate composite material shows that apparently higher than the analog value of unmodified resin the toughness of carbon nanotube/cyanate composite material has obtained improving well.
Referring to accompanying drawing 12, be the flexural strength column comparison diagram of the bisphenol A cyanate ester resin that provides of the carbon nanotube/cyanate composite material that provides of the embodiment of the invention 3,4 and 5 and Comparative Examples.Result by Figure 12 shows that the flexural strength of carbon nanotube/cyanate composite material shows that apparently higher than the analog value of unmodified resin the rigidity of carbon nanotube/cyanate composite material is significantly improved.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-amine propyl-triethoxysilicane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 18.9wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/cyanate composite material
Take by weighing surface-modified carbon nanotubes and 100g bisphenol A cyanate ester that the 2.3g above-mentioned steps obtains, they are mixed under 90 ℃ temperature condition, promptly obtain carbon nanotube/cyanate composite material.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-amine propyl-triethoxysilicane and 2.5g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 17.9wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/cyanate composite material
Take by weighing surface-modified carbon nanotubes and 60g bisphenol A cyanate ester and 40g dicyclopentadiene type ethylene rhodanate that the 1.1g above-mentioned steps obtains; They are mixed under 100 ℃ temperature condition, promptly obtain carbon nanotube/cyanate composite material and preparation method thereof.
1, contains the synthetic of phospho hetero phenanthrene structure and amine 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-aminocarbonyl propyl Trimethoxy silane of phospho hetero phenanthrene structure and hydroxyl; After 4.0g γ-amine propyl-triethoxysilicane and 2.2g zero(ppm) water mix; 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 superbranching ZGK 5 of containing, percentage of grafting is 18.3wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nano tube/epoxy resin matrix material
Take by weighing the surface-modified carbon nanotubes that the 2.7g above-mentioned steps obtains; 94g epoxy resin E51 (oxirane value is 0.51) is heated to 95 ℃ makes it to become low-viscosity (mobile) liquid; Ultra-sonic dispersion 0.5 hour; Add 10g solidifying agent two amido ditans, stir, promptly obtain carbon nanotube/epoxy composite material.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.7g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 18.5wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nano tube/epoxy resin matrix material
Take by weighing the surface-modified carbon nanotubes that the 2.3g above-mentioned steps obtains, 90g epoxy resin E51 is heated to 80 ℃ and makes it to become low-viscosity (mobile) liquid, and ultra-sonic dispersion 0.5 hour adds the 10g curing agent ethylene diamine, stirs, and promptly obtains carbon nanotube/epoxy composite material.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.8g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 18.7wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/bismaleimides/ethylene rhodanate/epoxide resin matrix material
Take by weighing surface-modified carbon nanotubes and 52g N that the 3g above-mentioned steps obtains; A N-penylene bismaleimides, 35g dihydroxyphenyl propane cyanate, 13g epoxy resin E44; They are mixed under 110 ℃ temperature condition, promptly obtain carbon nanotube/bismaleimides/ethylene rhodanate/epoxide resin matrix material
Embodiment 11
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.5g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 19.0wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/ethylene rhodanate/epoxide resin matrix material
Take by weighing surface-modified carbon nanotubes and 50g bisphenol A cyanate ester, 40g dicyclopentadiene type ethylene rhodanate and 10g epoxy resin E51 that the 1.1g above-mentioned steps obtains; They are mixed under 100 ℃ temperature condition, promptly obtain carbon nanotube/ethylene rhodanate/epoxide resin matrix material and preparation method thereof.
Embodiment 12
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 19.1wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/bismaleimides/cyanate composite material
Take by weighing surface-modified carbon nanotubes and 50g N that the 1.7g above-mentioned steps obtains; N'-(4; The 4'-methylenediphenyl) bismaleimides and 43g dicyclopentadiene type ethylene rhodanate; They are mixed under 120 ℃ temperature condition, promptly obtain carbon nanotube/bismaleimides/cyanate composite material.
Embodiment 13
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5.
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-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 19.4wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/bismaleimide resin composite material
53g N; N'-(4; The 4'-methylenediphenyl) the adjacent diallyl bisphenol of bismaleimides and 40g is behind 135 ℃ of pre-polymerization 30min; Add the surface-modified carbon nanotubes that the 1.7g above-mentioned steps obtains, they are mixed under 120 ℃ temperature condition, promptly obtain carbon nanotube/Bismaleimide composites.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 19.1wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/bismaleimide resin composite material
55g N; N'-(4; The 4'-methylenediphenyl) the adjacent diallyl bisphenol of bismaleimides and 41g is behind 135 ℃ of pre-polymerization 30min; Add the surface-modified carbon nanotubes that the 1.7g above-mentioned steps obtains, they are mixed under 120 ℃ temperature condition, promptly obtain carbon nanotube/Bismaleimide composites.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 19.6wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nano tube/epoxy resin matrix material
Take by weighing the surface-modified carbon nanotubes that the 2.5g above-mentioned steps obtains; 100g epoxy resin E44 is heated to 85 ℃ and makes it to become low-viscosity (mobile) liquid, and ultra-sonic dispersion 1 hour adds the 26g curing agent dicyandiamide; Stir, promptly obtain the carbon nano tube/epoxy resin matrix material.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 19.7wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/Bismaleimide composites
58g N; N'-(4; The 4'-methylenediphenyl) the adjacent diallyl bisphenol of bismaleimides and 45g is behind 135 ℃ of pre-polymerization 30min; Take by weighing the surface-modified carbon nanotubes that the 1.9g above-mentioned steps obtains, they are mixed under 120 ℃ temperature condition, promptly obtain carbon nanotube/Bismaleimide composites.
Embodiment 17
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.2g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 19.8wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/bismaleimides/cyanate ester resin composite material
Take by weighing surface-modified carbon nanotubes and 52g N that the 3g above-mentioned steps obtains; A N-penylene bismaleimides and 48g dihydroxyphenyl propane cyanate; They are mixed under 110 ℃ temperature condition, promptly obtain carbon nanotube/bismaleimides/cyanate ester resin composite material.
1, contains the synthetic of phospho hetero phenanthrene structure and amino superbranching ZGK 5
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-aminocarbonyl propyl Trimethoxy silane and 2.8g zero(ppm) water that contain phospho hetero phenanthrene structure and hydroxyl and mixing, 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 superbranching ZGK 5 of containing, percentage of grafting is 19.9wt%.
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 the amino superbranching ZGK 5; 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.
3, the preparation of carbon nanotube/ethylene rhodanate/epoxide resin matrix material
Take by weighing surface-modified carbon nanotubes and 70g bisphenol A cyanate ester and 23g epoxy resin E51 that the 2.4g above-mentioned steps obtains, they are mixed under 90 ℃ temperature condition, promptly obtain carbon nanotube/ethylene rhodanate/epoxide resin matrix material.
Claims (6)
1. carbon nanotube/thermoset ting resin composite, it is characterized in that: by weight, it comprises 100 parts of thermosetting resins and 0.2～4 part of surface-modified carbon nanotubes; Described surface-modified carbon nanotubes is the form grafted modified ultra-branching ZGK 5 of carbon nano tube surface with chemical bond, and its percentage of grafting is 15.0wt%～20.0wt%; Described surface-treated hyperbranched polyorganosiloxane contains the hyperbranched polyorganosiloxane of phospho hetero phenanthrene structure and amido for the surface.
2. a kind of carbon nanotube/thermoset ting resin composite according to claim 1 is characterized in that: described thermosetting resin is cyanate ester resin, bimaleimide resin, epoxy resin, or their arbitrary combination.
3. the preparation method of a carbon nanotube/thermoset ting resin composite 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 of amino-contained 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 surface-treated hyperbranched poly silane that contains phospho hetero phenanthrene structure and amido; 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 surface-treated hyperbranched polyorganosiloxane that step (2) is made mixes with the epoxide function carbon nano tube, supersound process 0.5～2 hour; 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;
(4) by weight, the surface-modified carbon nanotubes that 100 parts of thermosetting resins and 0.25～4 part of step (3) are obtained mixes under thermosetting resin fused temperature, obtains a kind of carbon nanotube/thermoset ting resin composite.
4. the preparation method of a kind of carbon nanotube/thermoset ting resin composite according to claim 3; 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.
5. the preparation method of a kind of carbon nanotube/thermoset ting resin composite according to claim 3; It is characterized in that: the trialkoxy silane of described amino-contained is a 3-aminocarbonyl propyl Trimethoxy silane; γ-amine propyl-triethoxysilicane, or their arbitrary combination.
6. the preparation method of a kind of carbon nanotube/thermoset ting resin composite according to claim 3, 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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