CN102863779A - Preparation method of composite material of interpenetrating polymer network and carbon nanotubes - Google Patents
Preparation method of composite material of interpenetrating polymer network and carbon nanotubes Download PDFInfo
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- CN102863779A CN102863779A CN201210396954XA CN201210396954A CN102863779A CN 102863779 A CN102863779 A CN 102863779A CN 201210396954X A CN201210396954X A CN 201210396954XA CN 201210396954 A CN201210396954 A CN 201210396954A CN 102863779 A CN102863779 A CN 102863779A
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Abstract
The invention relates to a preparation method of a composite material of an interpenetrating polymer network and carbon nanotubes, belonging to the technical field of the preparation of interpenetrating compounds. According to the invention, the preparation method uses castor oil as a raw material for synthesizing polyurethane and comprises the steps of: dispersing carbon tubes into the castor oil to form a stable suspension system, preparing polyurethane prepolymer through an in-situ polymerization method, and further penetrating with epoxy resin to prepare the polyurethane/epoxy resin interpenetrating polymer network composite material based on the in-situ composite of carbon nanotubes and renewable resources. The composite material prepared by the method has the advantages of uniformly dispersed carbon nanotubes, and obviously increased glass transition temperature, tensile strength and Young modulus, especially the Young modulus at a high temperature. Compared with the simple polyurethane/epoxy resin interpenetrating network material, the comprehensive properties of the composite material are more excellent. In addition, the properties of the interpenetrating network composite material can be designed and controlled though changing the concentration of carbon nanotubes and the functional groups on the carbon nanotubes.
Description
Technical field
The present invention relates to the preparing technical field of interpenetrating(polymer)networks mixture.
Background technology
Interpenetrating(polymer)networks mixture (IPN) is that two or more cross-linked polymer runs through and the polymer network that interweaves that forms mutually, can be regarded as a kind of technology that realizes the polymer physics blend with the method for chemistry, realize evenly running through on the molecular level by forcing between the interpenetrating(polymer)networks to dissolve each other, thereby make matrix material have simultaneously the advantageous property that forms each component of interpenetrating(polymer)networks.Polyurethane/epoxy resin Interpenetrating Networks mixture is the relatively more popular and ripe field of studying in the interpenetrating(polymer)networks, polyurethane/epoxy resin Interpenetrating Networks mixture can combine high strength, the high stable performance of high tenacity, snappiness and the Resins, epoxy of urethane, thereby the performance of matrix material is improved greatly, and Application Areas is widened greatly.But polyester polyol or the polyether glycol of preparation urethane all depend on petroleum resources, this non-renewable preparation and the application that has limited based on the Acrylic Polymer Interpenetrating Polymer of urethane strongly.Therefore, seek new, reproducible urethane synthesis material and urgently can not treat, and Viscotrol C a kind of like this raw material of excellence just.The hydroxyl that enriches in the Viscotrol C molecule and two keys provide possibility for its polyol component as urethane raw, also provide possibility for further modified polyurethane.
Carbon nanotube is a kind of novel nano material that emerges in recent years.Larger length-to-diameter ratio and excellent mechanical strength make it become the Nano filling of new generation of filling modification of polymer materials.If even carbon nanotube can be distributed in the polyurethane/epoxy resin Interpenetrating Networks material, just might utilize on the one hand the inner urethane of nanostructure enhancing interpenetrating(polymer)networks of carbon nanotube and the combination of Resins, epoxy; On the other hand, the mechanical property of carbon nanotube excellence also may improve the intensity of matrix material; In addition, the electroconductibility of carbon nanotube also may be given certain conductive capability of matrix material, thereby makes it have more wide application potential.
But the great specific surface area of carbon nanotube makes its surface energy high, is difficult for the dispersion of dissociating in macromolecule matrix.Melt-blending process or solution blended process commonly used all can not make carbon nanotube well be dispersed in the substrate medium at present, so this is also restricting carbon nanotube as macromolecular material, the especially application of the reinforcing filler of polymer Acrylic Polymer Interpenetrating Polymer.
Summary of the invention
The present invention seeks to propose a kind of composite manufacture method that improves polymer interpenetration network and the carbon nanotube of the dispersed homogeneous degree of carbon nanotube in the matrix material.
Technical scheme of the present invention is: Viscotrol C and carbon nanotube are mixed formation suspension system; In described suspension system, adopt first the compound base polyurethane prepolymer for use as of method synthesizing carbon nanotubes original position of in-situ polymerization, and then the base polyurethane prepolymer for use as that the carbon nanotube original position is compound is with after Resins, epoxy mixes, under the effect of chainextender, catalyzer and solidifying agent, further the reaction preparation can obtain the matrix material of polymer interpenetration network and carbon nanotube.
The present invention at first utilizes reproducible Biological resources---and Viscotrol C is as the raw material of synthesis of polyurethane, then carbon nanotube dispersed is become stable suspension system in Viscotrol C, utilize situ aggregation method to prepare base polyurethane prepolymer for use as, again further with Resins, epoxy IPN, the preparation carbon nanotube original position compound polyurethane/epoxy resin Interpenetrating Networks matrix material based on renewable resources.The matrix material that utilizes this method to make, being uniformly dispersed of carbon nanotube, the second-order transition temperature of material, tensile strength and Young's modulus, particularly the Young's modulus under the high temperature all significantly improves, compare with simple polyurethane/epoxy resin Interpenetrating Networks material, the over-all properties of matrix material is more excellent.In addition, by changing carbon nanotube concentration and surface functional group thereof, can also design and control the performance of interpenetrating(polymer)networks matrix material.
Key of the present invention is: the method by in-situ polymerization is compound to carbon nanotube in the middle of the Acrylic Polymer Interpenetrating Polymer, thereby improves distribution and the dispersion key that be technical solution of the present invention of carbon nanotube in matrix.This wherein at first is mixed into stable suspension system with carbon nanotube and Viscotrol C, and prepares the gordian technique that the compound base polyurethane prepolymer for use as of carbon nanotube original position is realization carbon nanotube good distribution in the interpenetrating(polymer)networks matrix.
The product that the present invention makes is special excellent to be:
(1) by selecting the renewable resources Viscotrol C as one of monomer for preparing urethane; effectively alleviated the energy shortage problem that causes owing to oil crisis; simultaneously; as a kind of material of polyfunctional group, two keys and hydroxyl abundant on the Viscotrol C molecule provide possibility for the further modification that realizes urethane.
(2) utilize ipn technology to obtain the matrix material of urethane and Resins, epoxy, effectively combine bi-material advantage separately, remedied the deficiency as one-component; On this basis further combined with the characteristics of high strength and modulus of carbon nanotube, thereby promoted greatly the performance of polyurethane/epoxy resin Interpenetrating Networks.
(3) carbon nanotube is uniformly dispersed, the second-order transition temperature of material, tensile strength and Young's modulus, particularly the Young's modulus under the high temperature all significantly improves, and compares with simple polyurethane/epoxy resin Interpenetrating Networks material, and the over-all properties of matrix material is more excellent.
(4) by changing carbon nanotube concentration and surface functional group thereof, can also design and control the performance of interpenetrating(polymer)networks matrix material.This not only provides a kind of method for the interpenetrating(polymer)networks composite materials of preparation nanoparticle uniform filling, also provides possibility for the application of expanding the polymer interpenetration network material.
In addition, the mixing quality of Viscotrol C of the present invention and carbon nanotube ratio is 0.2～4 ︰ 100.Such as the very few reinforced effects that is unfavorable for bringing into play self of the add-on of carbon nanotube, but the viscosity that again can greatly increase mixed system excessive such as the add-on of carbon nanotube, so that the cast molding in later stage is difficult for implementing.The mixing quality of control Viscotrol C and carbon nanotube 0.2～4 ︰ 100 is than then realizing comparatively significantly enhancing in the situation that do not affect moulding.
After the present invention mixes Viscotrol C and carbon nanotube, on magnetic stirring apparatus, stir 24h, and after the temperature that keeps suspension system is 60～65 ℃, again in the presence of solvent xylene, drip toluene 2, then the 4-vulcabond is stirring reaction under 65 ℃ the condition at temperature of reaction system, obtains the compound base polyurethane prepolymer for use as of carbon nanotube original position.As a rule the higher speed of response of temperature of reaction is faster, and the viscosity of system can sharply increase, and can't guarantee that on the one hand the dispersion of even carbon nanotube and original position are compound, also is unfavorable on the other hand follow-up cast molding step; But reaction temperature is spent to hang down and can so that the reaction times is long, be unfavorable for the raising of production efficiency again.Therefore consider to be chosen under 65 ℃ of temperature and react.
The described toluene 2 that drips, the mol ratio of the hydroxyl of Viscotrol C is 9 ︰ 4 in the isocyano in the 4-vulcabond and the suspension system.Isocyano-content is larger in the base polyurethane prepolymer for use as, system viscosity is lower, but isocyano amount free in the goods is also just more, for equilibrium viscosity and residual volume, the preferred toluene 2 of the present invention, the mol ratio of the hydroxyl of Viscotrol C is 9 ︰ 4 in isocyano in the 4-vulcabond and the suspension system, thereby has made the suitable performed polymer of system viscosity, and the composite property behind the curing molding is the most excellent in this case.
In the reaction system of the compound base polyurethane prepolymer for use as of synthesizing carbon nanotubes original position, the mass ratio that feeds intake of dimethylbenzene and Viscotrol C is 2～3 ︰ 10.The viscosity that this mass ratio that feeds intake has guaranteed system on the one hand is comparatively moderate, and carbon nanotube is better disperseed, and has also guaranteed on the other hand the balance between solvent removal and system solidify in the later stage cast molding step.
After adding dimethylbenzene, with cell ultrasonication instrument supersound process 20min, and then drip toluene 2,4-vulcabond.The ultrasonic efficient that cell ultrasonication instrument is higher can make carbon nanotube reach preferably dispersion effect within the shorter time, shortens the time of whole preparation process, enhances productivity.
The base polyurethane prepolymer for use as that described carbon nanotube original position is compound is with after Resins, epoxy mixes, temperature is to stir under 65 ℃ the condition in reaction system, add chainextender 1,4-butyleneglycol, catalyzer dibutyl tin dilaurate and solidifying agent triethylamine are evacuated to 0.1MPa, degassed 8～10min behind stirring 3～5min, at last with reaction system after solidifying 6h under 120 ℃ of conditions, be cooled to 60 ℃ again and solidify 12h, cooling and demolding namely gets the matrix material of polymer interpenetration network and carbon nanotube.Add chainextender, stirring 3～5min after catalyzer and the solidifying agent is in order to guarantee that itself and system mix; Degassed 8～10min can guarantee that solvent xylene removes from system substantially; When system viscosity increases, be poured in the mould simultaneously, obtain matrix material and can guarantee base polyurethane prepolymer for use as and each self cure IPN of Resins, epoxy thereby solidify 6h under 120 ℃ of conditions; Be cooled to 60 ℃ of continuation curing 12h and can guarantee that material internal solidifies fully.
In order to make the best comprehensive mechanical property of having of prepared matrix material, when the compound base polyurethane prepolymer for use as of described carbon nanotube original position mixed with Resins, epoxy, the mass ratio that feeds intake of the base polyurethane prepolymer for use as that the carbon nanotube original position is compound and Resins, epoxy was 70～30.
Description of drawings
Fig. 1 is the infrared spectrum of urethane, Resins, epoxy and polyurethane/epoxy resin.
Fig. 2 is the dissipation factor curve of the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of the carbon nanotube original position of different content of carbon nanotubes.
The stress-strain(ed) curve of the polyurethane/epoxy resin Interpenetrating Networks matrix material that the carbon nanotube original position of the different content of carbon nanotubes of Fig. 3 is compound.
Fig. 4 is the pattern sample environment stereoscan photograph of the brittle failure face of simple polyurethane/epoxy resin Interpenetrating Networks mixture.
Fig. 5 is the pattern sample environment stereoscan photograph of the brittle failure face of the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of carbon nanotube original position.
Fig. 6 is the field emission scanning electron microscope photo of brittle failure face of the sample of embodiment 4 preparation, and magnification is 20,000 times.
Fig. 7 is the field emission scanning electron microscope photo of brittle failure face of the sample of embodiment 4 preparation, and magnification is 50,000 times.
Embodiment
The present invention will be further described below in conjunction with example, but be not limited only to embodiment, below the explanation of each feature of raw material:
1, Viscotrol C: hydroxyl value is 163mgKOH/g, and average functionality is 2.7, and chemical pure is dewatered through underpressure distillation before using.
2, Resins, epoxy: oxirane value is 0.48～0.54/100g, and chemical pure is dewatered through underpressure distillation before using.
3, dimethylbenzene, BDO, dibutyl tin dilaurate and triethylamine are analytical pure, and be all dry through purifying before the use.
4, carbon nanotube: be carbon nanotube (CNT), carboxylic carbon nano-tube (CNT-COOH) or the hydroxylation carbon nanotube (CNT-OH) of purifying, internal diameter is about 10～20nm, external diameter is about 30～50nm, length is about 10～30 μ m, three's purity is all greater than 95wt%, and wherein the content of carboxylated and hydroxylated carbon nano tube surface carboxyl and hydroxyl is respectively 1.02wt% and 3.06wt%.
One, embodiment 1, polyurethane/epoxy resin=50/50(weight ratio) the preparation of interpenetrating(polymer)networks mixture:
1, the ratio take mass ratio as 100 ︰ 24 adds in the there-necked flask with Viscotrol C and dimethylbenzene, and mixing and stirring is put into oil bath with there-necked flask and is heated to 60～65 ℃.
2, in above there-necked flask, press toluene 2, in the 4-vulcabond in isocyano and the Viscotrol C mol ratio of hydroxyl be the ratio of 2.25 ︰ 1, constant speed drips toluene 2 in 20min, the 4-vulcabond, continue to keep 65 ℃ to continue to stir 60min, reaction obtains base polyurethane prepolymer for use as.
3, be that the proportioning of 50 ︰ 50 adds Resins, epoxy, 65 ℃ of lower rapid stirring mixing 20min according to base polyurethane prepolymer for use as and Resins, epoxy quality in the above there-necked flask again.
4, be that the ratio of 1 ︰ 1 adds 1 according to the mol ratio of residual isocyano and hydroxyl in the above there-necked flask again, the 4-butyleneglycol is as chainextender, and add successively in the system dibutyl tin dilaurate that accounts for urethane quality 1% as catalyzer with account for Resins, epoxy quality 1% triethylamine as solidifying agent, be evacuated to negative pressure 0.1MPa behind rapid stirring 3～5min, degassed 8～10min.
5, degassed reaction system is poured in the mould that is coated with releasing agent of preheating, behind 120 ℃ of curing 6h, be cooled to 60 ℃ and solidify 12h, get final product to get polyurethane/epoxy resin Interpenetrating Networks material after the cooling and demolding.
The infrared spectrum of embodiment 1 as shown in Figure 1.
As seen from Figure 1, add after the Resins, epoxy 3300cm
-1About absorption peak weaken 1500 cm
-1About urea key absorption peak weaken 830cm
-1About absorption peak significantly weaken, this has confirmed that Resins, epoxy and urethane have formed the IPN structure of certain cross-linking density.
Two, embodiment 2, polyurethane/epoxy resin=70/30(weight ratio) preparation of interpenetrating(polymer)networks mixture:
1, the ratio take mass ratio as 100 ︰ 24 adds in the there-necked flask with Viscotrol C and dimethylbenzene, and mixing and stirring is put into oil bath with there-necked flask and is heated to 60～65 ℃.
2, in above there-necked flask, press toluene 2, in the 4-vulcabond in isocyano and the Viscotrol C mol ratio of hydroxyl be the ratio of 2.25 ︰ 1, constant speed drips toluene 2 in 20min, the 4-vulcabond, continue to keep 65 ℃ to continue to stir 60min, reaction obtains base polyurethane prepolymer for use as.
3, be that the proportioning of 70 ︰ 30 adds Resins, epoxy, 65 ℃ of lower rapid stirring mixing 20min according to base polyurethane prepolymer for use as and Resins, epoxy quality in the above there-necked flask again.
4, be that the ratio of 1 ︰ 1 adds 1 according to the mol ratio of residual isocyano and hydroxyl in the above there-necked flask again, the 4-butyleneglycol is as chainextender, and add successively in the system dibutyl tin dilaurate that accounts for urethane quality 1% as catalyzer with account for Resins, epoxy quality 1% triethylamine as solidifying agent, be evacuated to negative pressure 0.1MPa behind rapid stirring 3～5min, degassed 8～10min.
5, degassed reaction system is poured in the mould that is coated with releasing agent of preheating, behind 120 ℃ of curing 6h, be cooled to 60 ℃ and solidify 12h, get final product to get polyurethane/epoxy resin Interpenetrating Networks material after the cooling and demolding.
Three, embodiment 3, and content is compound polyurethane/epoxy resin (the quality proportioning is 70/30) the interpenetrating(polymer)networks composite manufacture of carbon nanotube original position of the purifying of 0.1wt%:
1, the carbon nanotube and the Viscotrol C that add a certain amount of purifying in the there-necked flask, wherein the mass ratio of the carbon nanotube of purifying and Viscotrol C is 1 ︰ 500, mix 24h at the heat-collecting magnetic stirring device, keeping oil bath temperature is 60～65 ℃, obtains the suspension system of uniform Viscotrol C and carbon nanotube; And then add dimethylbenzene (it is 24 ︰ 100 that the quality of dimethylbenzene and Viscotrol C is joined), mix rear with the ultrasonic 20min(of cell ultrasonication instrument ultrasonic pitch time be 2s).
2, in above there-necked flask, press toluene 2, in the 4-vulcabond in isocyano and the suspension system ratio of the hydroxyl mole of Viscotrol C be the ratio of 9 ︰ 4, constant speed drips toluene 2 in 20min, the 4-vulcabond, continue to keep 65 ℃ to continue to stir 60min, reaction obtains the compound base polyurethane prepolymer for use as of carbon nanotube original position.
3, be that the ratio of 70 ︰ 30 adds Resins, epoxy, 65 ℃ of lower rapid stirring mixing 20min according to the compound base polyurethane prepolymer for use as of carbon nanotube original position and Resins, epoxy mass ratio in the there-necked flask again.
4, be that the ratio of 1 ︰ 1 adds 1 according to the mol ratio of residual isocyano and hydroxyl in the there-necked flask, the 4-butyleneglycol is as chainextender, and add successively in the system dibutyl tin dilaurate that accounts for urethane quality 1% as catalyzer with account for Resins, epoxy quality 1% triethylamine as solidifying agent, be evacuated to negative pressure 0.1MPa behind rapid stirring 3～5min, degassed 8～10min;
5, degassed reaction system is poured in the mould that is coated with releasing agent of preheating, be cooled to 60 ℃ and solidify 12h behind 120 ℃ of curing 6h, cooling and demolding namely gets the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of carbon nanotube original position.
Four, embodiment 4, and content is compound polyurethane/epoxy resin (the quality proportioning is 70/30) the interpenetrating(polymer)networks composite manufacture of carbon nanotube original position of the purifying of 0.5wt%:
1, the carbon nanotube and the Viscotrol C that add a certain amount of purifying in the there-necked flask, wherein the mass ratio of the carbon nanotube of purifying and Viscotrol C is 1 ︰ 100, mix 24h at the heat-collecting magnetic stirring device, keeping oil bath temperature is 60～65 ℃, obtains the suspension system of uniform Viscotrol C and carbon nanotube; And then add dimethylbenzene (it is 24 ︰ 100 that the quality of dimethylbenzene and Viscotrol C is joined), mix rear with the ultrasonic 20min(of cell ultrasonication instrument ultrasonic pitch time be 2s).
2, in above there-necked flask, press toluene 2, in the 4-vulcabond in isocyano and the suspension system ratio of the hydroxyl mole of Viscotrol C be the ratio of 9 ︰ 4, constant speed drips toluene 2 in 20min, the 4-vulcabond, continue to keep 65 ℃ to continue to stir 60min, reaction obtains the compound base polyurethane prepolymer for use as of carbon nanotube original position.
3, be that the ratio of 70 ︰ 30 adds Resins, epoxy, 65 ℃ of lower rapid stirring mixing 20min according to the compound base polyurethane prepolymer for use as of carbon nanotube original position and Resins, epoxy mass ratio in the there-necked flask again.
4, be that the ratio of 1 ︰ 1 adds 1 according to the mol ratio of residual isocyano and hydroxyl in the there-necked flask, the 4-butyleneglycol is as chainextender, and add successively in the system dibutyl tin dilaurate that accounts for urethane quality 1% as catalyzer with account for Resins, epoxy quality 1% triethylamine as solidifying agent, be evacuated to negative pressure 0.1MPa behind rapid stirring 3～5min, degassed 8～10min;
5, degassed reaction system is poured in the mould that is coated with releasing agent of preheating, be cooled to 60 ℃ and solidify 12h behind 120 ℃ of curing 6h, cooling and demolding namely gets the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of carbon nanotube original position.
Can see the zone that does not occur agglomerating white bright spot (namely carbon nanotube reunion) publishing picture from Fig. 6,7, illustrate that carbon nanotube is very even in the dispersion of urethane and Epoxy Interpenetration Polymer Networks mixture, and the combination of carbon nanotube and matrix is also fine.
Five, embodiment 5, and content is compound polyurethane/epoxy resin (the quality proportioning is 70/30) the interpenetrating(polymer)networks composite manufacture of carbon nanotube original position of the purifying of 2wt%:
1, the carbon nanotube and the Viscotrol C that add a certain amount of purifying in the there-necked flask, wherein the mass ratio of the carbon nanotube of purifying and Viscotrol C is 4 ︰ 100, mix 24h at the heat-collecting magnetic stirring device, keeping oil bath temperature is 60～65 ℃, obtains the suspension system of uniform Viscotrol C and carbon nanotube; And then add dimethylbenzene (it is 24 ︰ 100 that the quality of dimethylbenzene and Viscotrol C is joined), mix rear with the ultrasonic 20min(of cell ultrasonication instrument ultrasonic pitch time be 2s).
2, in above there-necked flask, press toluene 2, in the 4-vulcabond in isocyano and the suspension system ratio of the hydroxyl mole of Viscotrol C be the ratio of 9 ︰ 4, constant speed drips toluene 2 in 20min, the 4-vulcabond, continue to keep 65 ℃ to continue to stir 60min, reaction obtains the compound base polyurethane prepolymer for use as of carbon nanotube original position.
3, be that the ratio of 70 ︰ 30 adds Resins, epoxy, 65 ℃ of lower rapid stirring mixing 20min according to the compound base polyurethane prepolymer for use as of carbon nanotube original position and Resins, epoxy mass ratio in the there-necked flask again.
4, be that the ratio of 1 ︰ 1 adds 1 according to the mol ratio of residual isocyano and hydroxyl in the there-necked flask, the 4-butyleneglycol is as chainextender, and add successively in the system dibutyl tin dilaurate that accounts for urethane quality 1% as catalyzer with account for Resins, epoxy quality 1% triethylamine as solidifying agent, be evacuated to negative pressure 0.1MPa behind rapid stirring 3～5min, degassed 8～10min;
5, degassed reaction system is poured in the mould that is coated with releasing agent of preheating, be cooled to 60 ℃ and solidify 12h behind 120 ℃ of curing 6h, cooling and demolding namely gets the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of carbon nanotube original position.
The second-order transition temperature of the sample of embodiment 3,4,5 preparations and stress-strain(ed) curve are shown in Fig. 2 and 3.
Along with the increase of content of carbon nanotubes, the second-order transition temperature of matrix material increases as seen from Figure 2.
Along with the increase of content of carbon nanotubes, the tensile strength of matrix material increases as seen from Figure 3, and elongation at break reduces.
Fig. 4 is the cross-section morphology of simple polyurethane/epoxy resin Interpenetrating Networks mixture.
Fig. 5 is that content of carbon nanotubes is the cross-section morphology of the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of the carbon nanotube original position of 0.5wt%.
From Fig. 4,5 as seen, the result shows that the section of matrix material is more even after the adding carbon nanotube, and the degree of dissolving each other of urethane and Resins, epoxy improves.
Six, embodiment 6, and content is compound polyurethane/epoxy resin (the quality proportioning is 70/30) the interpenetrating(polymer)networks composite manufacture of carbon nanotube original position of the purifying of 1wt%:
The carbon nanotube and the Viscotrol C that add first a certain amount of purifying in the there-necked flask, wherein the mass ratio of the carbon nanotube of purifying and Viscotrol C is 2 ︰ 100, mix 24h at the heat-collecting magnetic stirring device, keeping oil bath temperature is 60～65 ℃, obtains the suspension system of uniform Viscotrol C and carbon nanotube; And then add dimethylbenzene (it is 24 ︰ 100 that the quality of dimethylbenzene and Viscotrol C is joined), mix rear with the ultrasonic 20min(of cell ultrasonication instrument ultrasonic pitch time be 2s).
Make the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of carbon nanotube original position by 2,3,4,5 step among the embodiment 5 again.
Seven, embodiment 7, and content is the compound polyurethane/epoxy resin of the carbon nanotube functionalized with carboxylic acid group original position of 1wt% (the quality proportioning is 70/30) interpenetrating(polymer)networks composite manufacture:
In there-necked flask, add a certain amount of carbon nanotube functionalized with carboxylic acid group and Viscotrol C first, wherein the quality proportioning of carbon nanotube functionalized with carboxylic acid group and Viscotrol C is 2 ︰ 100, mix 24h at the heat-collecting magnetic stirring device, keeping oil bath temperature is 60～65 ℃, obtains the suspension system of uniform Viscotrol C and carbon nanotube; And then add dimethylbenzene (it is 24 ︰ 100 that the quality of dimethylbenzene and Viscotrol C is joined), mix rear with the ultrasonic 20min(of cell ultrasonication instrument ultrasonic pitch time be 2s).
Make the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of carbon nanotube original position by 2,3,4,5 step among the embodiment 5 again.
Eight, embodiment 8, and content is the compound polyurethane/epoxy resin of the hydroxylated carbon nanotube original position of 1wt% (the quality proportioning is 70/30) interpenetrating(polymer)networks composite manufacture:
The method same with example 7 prepares the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of carbon nanotube original position.
During embodiment 6,7,8 Young's modulus, tensile strength and elongation at break are listed in the table below.
| Sample | Modulus/MPa | Tensile strength/MPa | Maximum strain/% |
| Embodiment 7 | 12±2 | 9.68±0.16 | 190.2±1.8 |
| |
59±4 | 11.12±0.18 | 102.8±7.1 |
| Embodiment 8 | 8.5±0. 3 | 6.63±0.20 | 127.7±7.0 |
From upper table as seen: modulus, tensile strength and the maximum strain of the polyurethane/epoxy resin Interpenetrating Networks matrix material that the carbon nanotube original position of different surfaces functional group is compound are different.Wherein modulus and the tensile strength of the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of the pure carbon nanotube original position that does not contain any functional group are greater than the compound polyurethane/epoxy resin Interpenetrating Networks matrix material of carboxylated and hydroxylated carbon nanotube original position, but maximum strain is but less than the latter.In general, compare with carboxylated and hydroxylated carbon nanotube, the reinforced effects after the pure carbon nanotube that does not contain any functional group and polyurethane/epoxy resin Interpenetrating Networks material in situ are compound is better.
Claims (8)
1. the composite manufacture method of a polymer interpenetration network and carbon nanotube is characterized in that Viscotrol C and carbon nanotube mixed forming suspension system; In described suspension system, adopt first the compound base polyurethane prepolymer for use as of method synthesizing carbon nanotubes original position of in-situ polymerization, and then the base polyurethane prepolymer for use as that the carbon nanotube original position is compound is with after Resins, epoxy mixes, under the effect of chainextender, catalyzer and solidifying agent, further the reaction preparation can obtain the matrix material of polymer interpenetration network and carbon nanotube.
2. the composite manufacture method of described polymer interpenetration network and carbon nanotube according to claim 1, the mixing quality ratio that it is characterized in that described Viscotrol C and carbon nanotube is 0.2～4 ︰ 100.
3. the composite manufacture method of described polymer interpenetration network and carbon nanotube according to claim 1 and 2, it is characterized in that after Viscotrol C and the carbon nanotube mixing, on magnetic stirring apparatus, act on 24h, and after the temperature that keeps suspension system is 60～65 ℃, in the presence of solution dimethylbenzene, drip toluene 2, the 4-vulcabond again, then be stirring reaction under 65 ℃ the condition at temperature of reaction system, obtain the compound base polyurethane prepolymer for use as of carbon nanotube original position.
4. the composite manufacture method of described polymer interpenetration network and carbon nanotube according to claim 3 is characterized in that the described toluene 2 that drips, and the mol ratio of the hydroxyl of Viscotrol C is 9 ︰ 4 in the isocyano in the 4-vulcabond and the suspension system.
5. the composite manufacture method of described polymer interpenetration network and carbon nanotube according to claim 3, it is characterized in that in the reaction system of the compound base polyurethane prepolymer for use as of synthesizing carbon nanotubes original position, the mass ratio that feeds intake of dimethylbenzene and Viscotrol C is 2～3 ︰ 10.
6. according to claim 3 or the composite manufacture method of 5 described polymer interpenetration networks and carbon nanotube, it is characterized in that after adding dimethylbenzene, with cell ultrasonication instrument supersound process 20min, and then drip toluene 2,4-vulcabond.
7. the composite manufacture method of described polymer interpenetration network and carbon nanotube according to claim 1, after it is characterized in that the base polyurethane prepolymer for use as that described carbon nanotube original position is compound and Resins, epoxy mixing, temperature is to stir under 65 ℃ the condition in reaction system, add chainextender 1, the 4-butyleneglycol, catalyzer dibutyl tin dilaurate and solidifying agent triethylamine, be evacuated to 0.1MPa after stirring 3～5min, degassed 8～10min, at last with reaction system after solidifying 6h under 120 ℃ of conditions, be cooled to again 60 ℃ and solidify 12h, cooling and demolding namely gets the matrix material of polymer interpenetration network and carbon nanotube.
8. the composite manufacture method of described polymer interpenetration network and carbon nanotube according to claim 7, when it is characterized in that the compound base polyurethane prepolymer for use as of described carbon nanotube original position mixes with Resins, epoxy, the mass ratio that feeds intake of the base polyurethane prepolymer for use as that the carbon nanotube original position is compound and Resins, epoxy is 70～30.
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