CN104513354A - Preparation method of polyurethane composite containing carbon nanotube - Google Patents
Preparation method of polyurethane composite containing carbon nanotube Download PDFInfo
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Abstract
The invention relates to a carbon nanotube-polyurethane composite, and preparation method thereof. According to the invention, the polyurethane composite containing uniformly distributed carbon nanotubes, which can show improved electricity conductivity and mechanical performance, can be prepared with a simpler method.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane composition of carbon nanotubes.
Background technology
Urethane, as the polymer being applied to the various industrial circles such as automotive field, field of electronic materials, garment industry, paint field, needs the various physical property such as adjustment tensile strength, wear rate, unit elongation according to Application Areas.
Usually, high molecular physical property is adjusted by the mixing ratio of feed change or the method for mixing functions additive.Recently, attempt adjusting high molecular physical property by the carbon class materials such as compound carbon black, carbon nanotube, Graphene and polymer.
In described carbon class material, especially carbon nanotube has excellent thermal conductivity, electroconductibility, physical strength etc. as typical carbon nano structure, therefore just receives publicity as the material that can be applicable to various electrical element and high-strength nano mixture.
But carbon nanotube is wound around (entangled) together mutually by powerful Van der Waals force (van der Waals force), there is the problem that can not be scattered in equably in macromolecule medium.Therefore, attempt carbon nano tube surface and introduce the method that functional group carries out modification or employing multi-step physical process.But this method exists problems, such as need complicated preprocessing process to cause productivity to reduce, use the organic solvent to human body or bad environmental, and in the preprocessing process of carbon nanotube, the damage because of carbon nanotube causes physical property reduction etc.
Summary of the invention
The object of the present invention is to provide a kind of method can preparing the polyurethane composition being dispersed with carbon nanotube equably with a simpler process.
The present invention also aims to provide the carbon nano tube-polyurethane mixture that a kind of electroconductibility of being prepared by described method and mechanical property are improved.
According to the preparation method that the invention provides a kind of carbon nano tube-polyurethane complex body, comprising:
Preparation is mixed with the dispersion liquid of polyvalent alcohol (polyol) and autoregistration carbon nanotube (self-aligned carbonnanotube); With
Under the existence of chainextender, add diisocyanate cpd in described dispersion liquid and make it carry out polyreaction.
And, according to the preparation method that the invention provides a kind of carbon nano tube-polyurethane complex body, comprising: under the existence of chainextender, make the dispersion liquid comprising polyvalent alcohol, autoregistration carbon nanotube and diisocyanate cpd carry out polyreaction.
According to an embodiment, described dispersion liquid prepares by following methods: the composition comprising polyvalent alcohol and autoregistration carbon nanotube or the composition that comprises polyvalent alcohol, autoregistration carbon nanotube and diisocyanate cpd are mixed 30 ~ 300 minutes at bead mill (bead mill).
According to an embodiment, relative to the described polyvalent alcohol of 100 weight parts, the autoregistration carbon nanotube of 0.5 ~ 5 weight part, the chainextender of 1 ~ 10 weight part can be used, and the diisocyanate cpd of 5 ~ 30 weight parts.
According to an embodiment, described autoregistration carbon nanotube can comprise diameter to be 5 ~ 20nm and length be multiple carbon nanotubes of 1 ~ 600 μm.
According to an embodiment, described polyvalent alcohol can have the weight-average molecular weight of 500 ~ 10000.Described polyvalent alcohol can be more than one compounds be selected from PTMG (polytetramethylene glycol), polyoxyethylene glycol, polypropylene glycol and polycaprolactone glycol (polycaprolactone diol).
According to an embodiment, described diisocyanate cpd can be and is selected from 1, 6-hexamethylene diisocyanate (1, 6-hexamethylene diisocyanate), 4, 4 '-diphenylmethanediisocyanate (4, 4'-methylenediphenyl diisocyanate), isophorone diisocyanate (isophoronediisocyanate), 4, 4 '-two isocyanato-dicyclohexyl methyl hydride (4, 4'-diisocyanatodicyclohexylmethane), tetramethylene diisocyanate (tetramethylene diisocyanante), methyl pentamethylene diisocyanate (methylpentamethylene diisocyanate), ten dimethylene diisocyanates (dodecamethylene diisocyanate), 1, 4-cyclohexyl diisocyanate (1, 4-diisocyanato cyclohexane), 4, 4 '-two isocyanato-dicyclohexyl propane-(2, 2) (4, 4'-diisocyanato dicyclohexylpropane-(2, 2)), 1, 4-bis-isocyanato-benzene (1, 4-diisocyanato benzene), 2, 4-bis-isocyanato-toluene (2, 4-diisocyanatotoluene), 2, 6-bis-isocyanato-toluene (2, 6-diisocyanato toluene), two isocyanato-ditans (diisocyanato diphenylmethane), tetramethyl xylylen vulcabond (tetramethylxylene diisocyanate), p-xylyl diisocyanate (p-xylenediisocyanate), more than one compounds in p-isopropylidene vulcabond (p-isopropylidene diisocyanate).
According to an embodiment, described chainextender can be more than one compounds be selected from ethylene glycol, propylene glycol, butyleneglycol, pentanediol and hexylene glycol.
In addition, according to the carbon nano tube-polyurethane complex body of an embodiment, relative to the urethane of carbon nanotube (entangled carbon nanotube) compound tangling structure, the electroconductibility (S/cm) of increase by 10 ~ 10000 times can be had.
According to the carbon nano tube-polyurethane complex body of an embodiment, relative to the urethane of carbon nanotube compound tangling structure, the tensile strength (kgf/cm of increase by 10 ~ 100% can be had
2).
According to the carbon nano tube-polyurethane complex body of an embodiment, relative to the urethane of carbon nanotube compound tangling structure, the unit elongation (%) of increase by 50 ~ 400% can be had.
Can prepare the urethane complex body being dispersed with carbon nanotube equably with a simpler process according to the present invention, this complex body can demonstrate the electroconductibility and mechanical property that more improve.And described carbon nano tube-polyurethane is applicable to the various industrial circles such as automotive field, field of electronic materials, garment industry, paint field.
Accompanying drawing explanation
Fig. 1 is the photo with the carbon nanotube ((a) of Fig. 1) of scanning electronic microscope (SEM) amplifying observation autoregistration form and the carbon nanotube ((b) of Fig. 1) of winding form.
Fig. 2 is the photo with the carbon nano tube-polyurethane mixture ((a) of Fig. 2) of scanning electronic microscope (SEM) amplifying observation one embodiment of the invention and mixture ((b) of Fig. 2) surface of comparative example.
Embodiment
Below, describe in further detail according to the preparation method of the carbon nano tube-polyurethane mixture of the specific embodiment of the invention and the mixture prepared according to the method.
Unless there are clearly stating, the term used in entire description just for the object describing specific embodiment, and is not intended to limit the present invention.Unless clearly pointed out in addition in context, otherwise singulative used here is also intended to comprise plural form.It should also be understood that, term " comprises " and " comprising " is not specifically refer to some characteristic, field, integer, step, action, key element and/or composition, and gets rid of the existence or additional of other characteristics, field, integer, step, action, key element, composition and/or group.
Find in the process that the polyurethane composition of the present inventor to carbon nanotubes (hereinafter referred to as " CNT ") is studied repeatedly, relative to the common CNT being wound around form, even if the CNT of autoregistration form does not separately carry out pre-treatment, also outstanding dispersiveness is demonstrated to urethane.Accordingly, when using the CNT of autoregistration form, by better simply method without the need to separately carrying out pretreatment technology to CNT, the CNT-polyurethane composition that electroconductibility and mechanical property are significantly improved can be provided.
The preparation method of carbon nano tube-polyurethane mixture according to an embodiment of the invention, comprising:
Prepare the dispersion liquid being mixed with polyvalent alcohol and autoregistration carbon nanotube; With
Under the existence of chainextender, add diisocyanate cpd in described dispersion liquid and make it carry out polyreaction.
Below, each step of described preparation method is described in detail.
First, according to the preparation method of the CNT-polyurethane composition of an embodiment, can comprise: the dispersion liquid preparing to be mixed with polyvalent alcohol and autoregistration CNT.
Described polyvalent alcohol is the compound of more than 2 as hydroxyl equivalent in each molecule, by forming amino-formate bond with the reaction of isocyanate ester compound.In the present invention, described polyvalent alcohol can be the Conventional compounds for the formation of urethane, is not particularly limited this.Just, as nonrestrictive example, described polyvalent alcohol can be more than one compounds be selected from PTMG, polyoxyethylene glycol, polypropylene glycol and polycaprolactone glycol.And in order to ensure the mechanical property needed for urethane, the weight-average molecular weight of described polyvalent alcohol can be 500 ~ 10000 or 1000 ~ 5000 or 1000 ~ 4000 or 1500 ~ 3500 or 2000 ~ 3500.
On the one hand, as shown in Figure 1, described autoregistration CNT ((a) of Fig. 1) is different from the conventional CNT ((b) of Fig. 1) of winding arrangement, and to comprise diameter be a few nanometer to tens nanometer and length is several microns of self aligned multiple CNT bundles to hundreds of micron.Accordingly, when described autoregistration CNT mixes with polyvalent alcohol (medium), multiple CNT of bunchy can be scattered in polyvalent alcohol equably with the form of scattering.But the conventional CNT of winding arrangement is because Van der Waals force dispersiveness powerful between CNT reduces and forms coacervate.By contrast, even if described autoregistration CNT does not separately carry out pre-treatment (such as, the method of functional group is introduced in CNT surface) or adopt multistage physical dispersion method etc., also demonstrate outstanding dispersiveness, thus electrical property, mechanical property, thermal characteristics can be provided evenly and the mixture improved.
Multiple CNT can be used with the common autoregistration CNT of bunchy shape alignment as described autoregistration CNT, and the structures such as single wall CNT (single walled carbon nanotube), many walls CNT (multiwalled carbon nanotube) are not particularly limited.Just, according to an embodiment, described autoregistration CNT comprises diameter to be 5 ~ 20nm and length be multiple carbon nanotubes of 1 ~ 600 μm, are more conducive to characterizing and improve effect according to physical property of the present invention.
On the other hand, according to an embodiment, the dispersion liquid being mixed with described polyvalent alcohol and autoregistration CNT is by preparing in the method for bead mill mixing 30 ~ 300 minutes or 30 ~ 120 minutes or 30 ~ 90 minutes or 30 ~ 60 minutes.That is, described autoregistration CNT may limitedly characterize uniform dispersion state by conventional hybrid technique, but by being suitable for the optimum dispersion method as an above-mentioned embodiment, can prepare the dispersion liquid relative to the CNT of winding arrangement with outstanding dispersiveness.
Now, relative to the described polyvalent alcohol of 100 weight parts, the described autoregistration CNT of 0.5 ~ 5 weight part or 0.5 ~ 3.5 weight part or 1 ~ 3.5 weight part or 1 ~ 3 weight part can be comprised.That is, relative to the polyvalent alcohol of 100 weight parts, comprise the described autoregistration CNT of more than 0.5 weight part, be conducive to fully characterizing physical property of the presently claimed invention and improve effect.Just, if excessive interpolation CNT, then the dispersion state of CNT is deteriorated, and may form CNT coacervate in mixture, the mechanical property of mixture can reduce thus.Therefore, relative to the described polyvalent alcohol of 100 weight parts, comprise the described autoregistration CNT of below 5 weight parts advantageously.
And, hydrocarbon diluent can be comprised further in described dispersion liquid as required.Described hydrocarbon diluent optimizes the composition of the operability according to suitable application area as the viscosity by adjusting mixture, can be C
6~ C
10aliphatic hydrocarbon or aromatic hydrocarbons or its mixture.And, relative to the described polyvalent alcohol of 100 weight parts, the described hydrocarbon diluent of 0.5 ~ 5 weight part can be comprised.
On the other hand, according to the preparation method of the CNT-polyurethane composition of an embodiment, can comprise: under the existence of chainextender, add diisocyanate cpd in described dispersion liquid and make it carry out polyreaction.
That is, according to the preparation method of CNT-polyurethane composition of the present invention, except making described autoregistration CNT dispersion, can carry out by polyurethane Preparation Method routinely.
According to an embodiment, described diisocyanate cpd, as by forming the compound of amino-formate bond with the reaction of described polyvalent alcohol, can be the Conventional compounds for the formation of urethane, being not particularly limited this.Just, as nonrestrictive example, described diisocyanate cpd can be and is selected from 1, 6-hexamethylene diisocyanate, 4, 4 '-diphenylmethanediisocyanate, isophorone diisocyanate, 4, 4 '-two isocyanato-dicyclohexyl methyl hydride, tetramethylene diisocyanate, methyl pentamethylene diisocyanate, ten dimethylene diisocyanates, 1, 4-cyclohexyl diisocyanate, 4, 4 '-two isocyanato-dicyclohexyl propane-(2, 2), 1, 4-bis-isocyanato-benzene, 2, 4-bis-isocyanato-toluene, 2, 6-bis-isocyanato-toluene, two isocyanato-ditans, tetramethyl xylylen vulcabond, p-xylyl diisocyanate, more than one compounds in p-isopropylidene vulcabond.
Now, the content of described diisocyanate cpd is not particularly limited, and can consider to be determined with the equivalence ratio of described polyvalent alcohol, the urethane physical property etc. that will obtain.Just, according to an embodiment, relative to the described polyvalent alcohol of 100 weight parts, comprise the described diisocyanate cpd of 5 ~ 30 weight parts or 15 ~ 30 weight parts or 20 ~ 30 weight parts or 25 ~ 30 weight parts, may be conducive to guaranteeing sufficient physical property.
And described chainextender (chain extender) also can be the Conventional compounds for the formation of urethane, is not particularly limited this.Just, as nonrestrictive example, described chainextender can be more than one compounds be selected from ethylene glycol, propylene glycol, butyleneglycol, pentanediol and hexylene glycol.
The content of described chainextender is not particularly limited, and can consider that the physical property etc. of the urethane for being formed is determined.Just, according to an embodiment, relative to the described polyvalent alcohol of 100 weight parts, comprise the described chainextender of 1 ~ 10 weight part or 5 ~ 10 weight parts, may be conducive to guaranteeing sufficient physical property.
In addition, the organic solvents such as dimethyl formamide, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), dimethylbenzene, toluene, 1-Methyl-2-Pyrrolidone can be used in described polyreaction.Now, preferably, described organic solvent moisture-free.Reason is, if organic solvent comprises moisture, moisture and isocyanate group are carried out reaction and produced carbonic acid gas, may form the mixture no intention to the foam form formed thus.According to an embodiment, relative to the described polyvalent alcohol of 100 weight parts, the described organic solvent of 100 ~ 500 weight parts or 200 ~ 500 weight parts or 200 ~ 400 weight parts or 200 ~ 300 weight parts can be comprised.That is, when the content of organic solvent is low, cannot guarantee sufficient viscosity and be difficult to stir, when the too high levels of organic solvent, time of drying is elongated, and process efficiency can reduce, and therefore carries out adjusting advantageously in described scope.
And, may unreacted isocyanate group being contained in the mixture obtained by described polyreaction, in order to remove unreacted isocyanate group, the step that compounds such as adding dibutylamine carries out aftertreatment can also be performed.
On the one hand, the preparation method of the carbon nano tube-polyurethane mixture of another embodiment of the present invention, comprising: under the existence of chainextender, makes the dispersion liquid comprising polyvalent alcohol, autoregistration carbon nanotube and diisocyanate cpd carry out polyreaction.
That is, according to the preparation method of mixture of the present invention, undertaken by following methods: i) as previous embodiment, the another standby dispersion liquid being mixed with polyvalent alcohol and autoregistration CNT, and add diisocyanate cpd wherein and carry out polyreaction.And, according to the preparation method of mixture of the present invention, also undertaken by following methods: ii) polyreaction is carried out on polyvalent alcohol, autoregistration CNT and mixing limit, diisocyanate cpd limit.
Wherein, as previously mentioned, described dispersion liquid prepares by following methods: will comprise the composition of polyvalent alcohol, autoregistration carbon nanotube and diisocyanate cpd bead mill mixing 30 ~ 300 minutes.
To the explanation of described polyvalent alcohol, described autoregistration CNT, described diisocyanate cpd, described chainextender etc., also refer to foregoing teachings.
On the other hand, provide a kind of CNT-polyurethane composition according to another embodiment of the present invention, it comprises urethane and is dispersed in the CNT in described urethane.
Described mixture, as the mixture being dispersed with CNT in the matrix comprising urethane equably, is prepared by preceding method.As previously mentioned, use autoregistration CNT in the preparation method of described mixture, thus the dispersiveness of CNT is outstanding, can provide the mixture that electrical property, mechanical property, thermal characteristics unanimously improve.
According to an embodiment, the CNT-polyurethane composition prepared with preceding method, relative to the urethane using the conventional CNT of winding arrangement of identical amount to be composited, the electroconductibility of raising about 10 ~ 10000 times or about 50 ~ 10000 times or 70 ~ 10000 times or 70 ~ 9600 times can be demonstrated.
And, according to an embodiment, the CNT-polyurethane composition prepared with preceding method, relative to the urethane that the conventional CNT of the winding arrangement using identical amount is composited, can demonstrate the tensile strength (kgf/cm of raising about 10 ~ 100% or about 15 ~ 30% or 15 ~ 25%
2).
And the CNT-polyurethane composition prepared with preceding method not only has the tensile strength that is improved but also demonstrates outstanding unit elongation.Namely, according to an embodiment, the CNT-polyurethane composition prepared with preceding method, relative to the urethane that the conventional CNT of the winding arrangement using identical amount is composited, the unit elongation (%) of raising about 50 ~ 400% or about 100 ~ 200% or 100 ~ 150% can be demonstrated.
Especially, the CNT-polyurethane composition prepared with preceding method comprises CNT with the dispersity improved further, thus under rugged environment, also can effectively maintain outstanding physical property after keeping.According to an embodiment, by the described CNT-polyurethane composition tensile strength that keeping is measured after 2 weeks at about 80 DEG C and unit elongation, the tensile strength measured relative to the initial stage and unit elongation, can maintain more than 80% or more than 90%.
Just, the physical property of described CNT-polyurethane composition can change, as long as those skilled in the art in the invention just can adjust the physical property of mixture by described preparation method according to the structure of medium urethane, kind and molecular weight etc.
CNT-polyurethane composition of the present invention can effectively for various industrial circles such as automotive field, field of electronic materials, garment industry, paint field.
Below, the invention provides preferred embodiment to contribute to understanding.But following embodiment, just for illustrating the present invention, is not intended to limit the invention.
embodiment 1
By containing have an appointment 2 % by weight autoregistration CNT (manufacturers: Han Hua chemistry, ProductName: CM-250) and about 98 % by weight polyvalent alcohol (polypropylene glycol, weight-average molecular weight about 3000) composition with bead mill (bead 0.8 Φ) mixing about 60 minutes, thus prepare dispersion liquid.
Then, by 1 of the described dispersion liquid of about 80g, about 5g, the aliphatic diisocyanate (1 of 4-butyleneglycol, about 20g, 6-hexamethylene diisocyanate) and the dimethyl formamide of about 200g put into reactor, and stir about after 1 hour at normal temperatures, at about 70 DEG C, dry also reaction about 24 hours, obtains carbon nano tube polyurethane mixture in this approach.
embodiment 2
By containing have an appointment 3 % by weight autoregistration CNT (manufacturers: Han Hua chemistry, ProductName: CM-250), the polyvalent alcohol (polypropylene glycol of about 94 % by weight, weight-average molecular weight about 3000) and about 3 % by weight hydrocarbon diluent (carbonatoms is the aliphatic hydrocarbon compound of 6 ~ 10) composition bead mill (bead 0.8 Φ) mixing about 60 minutes, thus prepare dispersion liquid.
Then, by 1 of the described dispersion liquid of about 80g, about 5g, the aliphatic diisocyanate (1 of 4-butyleneglycol, about 20g, 6-hexamethylene diisocyanate) put into reactor, and stir about after 1 hour at normal temperatures, at about 70 DEG C, dry also reaction about 24 hours, obtains carbon nano tube polyurethane mixture in this approach.
embodiment 3
By the polyvalent alcohol (polypropylene glycol containing the 78g that has an appointment, weight-average molecular weight about 3000), about 5g 1, the aliphatic diisocyanate (1 of 4-butyleneglycol, about 20g, 6-hexamethylene diisocyanate), composition bead mill (the bead 0.8 Φ) mixing about 60 minutes of the autoregistration CNT (manufacturers: Han Hua chemistry, ProductName: CM-250) of the dimethyl formamide of about 200g and about 2g.Then, by described composition stir about 1 hour at normal temperatures, dry at about 70 DEG C afterwards and reaction about 24 hours, obtains carbon nano tube polyurethane mixture in this approach.
comparative example
Except the CNT (manufacturers: Han Hua chemistry, ProductName: CM-95) with winding arrangement substitutes outside described autoregistration CNT, obtain carbon nano tube-polyurethane mixture by the method identical with embodiment 1.
experimental example 1 (observing the dispersion state of carbon nanotube)
Carry out amplifying observation with the surface of scanning electronic microscope (SEM) to each mixture obtained by embodiment 1 and comparative example, and the results are shown in Fig. 2.
Be dispersed in can confirming even carbon nanotube in the mixture ((a) of Fig. 2) of embodiment 1 by Fig. 2.In contrast to this, in the mixture ((b) of Fig. 2) of comparative example, carbon nanotube is not disperseed equably.
experimental example 2 (measuring electroconductibility and mechanical property)
For each mixture obtained by embodiment and comparative example, measure electroconductibility and mechanical property by the following method, and the results are shown in following table 1.
1) electroconductibility (S/cm): the resistance of mixture that utilized LORESTA equipment by JIS-K6911 canonical measure, and measure mixture test piece specification, obtain electroconductibility with this.
2) tensile strength (kgf/cm
2) and unit elongation (%): each 10 of the test piece preparing the Type1 specification of ASTM D638.Mean value is obtained after measuring the initial stage tensile strength of 5 test pieces and unit elongation with Universal Testing Machine.Then, at about 80 DEG C, keeping residue 5 test pieces 2 weeks, measure tensile strength and unit elongation by identical method afterwards.
[table 1]
Confirmed by upper table 1, there is relative to the mixture of comparative example according to the mixture of embodiment 1 ~ 3 electroconductibility of increase about 70 times ~ 9500 times.Also confirm the tensile strength demonstrating increase about 18% ~ 25% according to the mixture of embodiment 1 ~ 3 relative to the mixture of comparative example, and initial stage unit elongation improves about about 100 ~ 140%.As mentioned above, the mixture confirming these embodiments prepared with autoregistration CNT has the electrical property and mechanical property that significantly improve relative to the mixture of the comparative example prepared with the CNT of winding arrangement.
And confirm after taking care of under rugged environment according to the mixture of embodiment 1 ~ 3, its physical property also can maintain about more than 94% relative to initial stage physical property, and relative to initial stage physical property, the level that can maintain about 80% reaches more than about 4 weeks.
Claims (13)
1. a preparation method for carbon nano tube-polyurethane mixture, comprising:
Prepare the dispersion liquid being mixed with polyvalent alcohol and autoregistration carbon nanotube; With
Under the existence of chainextender, add diisocyanate cpd in described dispersion liquid and make it carry out polyreaction.
2. a preparation method for carbon nano tube-polyurethane mixture, comprising:
Under the existence of chainextender, the dispersion liquid comprising polyvalent alcohol, autoregistration carbon nanotube and diisocyanate cpd is made to carry out polyreaction.
3. the preparation method of the carbon nano tube-polyurethane mixture according to claims 1 or 2, wherein,
Described dispersion liquid is prepared bead mill mixing 30 ~ 300 minutes the composition comprising polyvalent alcohol and autoregistration carbon nanotube or the composition that comprises polyvalent alcohol, autoregistration carbon nanotube and diisocyanate cpd.
4. the preparation method of the carbon nano tube-polyurethane mixture according to claims 1 or 2, wherein,
Relative to polyvalent alcohol described in 100 weight parts, use 0.5 ~ 5 weight part autoregistration carbon nanotube, 1 ~ 10 weight part chainextender, and 5 ~ 30 weight part diisocyanate cpds.
5. the preparation method of the carbon nano tube-polyurethane mixture according to claims 1 or 2, wherein,
Described autoregistration carbon nanotube comprises diameter to be 5 ~ 20nm and length be multiple carbon nanotubes of 1 ~ 600 μm.
6. the preparation method of the carbon nano tube-polyurethane mixture according to claims 1 or 2, wherein,
Described polyvalent alcohol has the weight-average molecular weight of 500 ~ 10000.
7. the preparation method of the carbon nano tube-polyurethane mixture according to claims 1 or 2, wherein,
Described polyvalent alcohol is more than one compounds be selected from PTMG, polyoxyethylene glycol, polypropylene glycol and polycaprolactone glycol.
8. the preparation method of the carbon nano tube-polyurethane mixture according to claims 1 or 2, wherein,
Described diisocyanate cpd is for being selected from 1, 6-hexamethylene diisocyanate, 4, 4 '-diphenylmethanediisocyanate, isophorone diisocyanate, 4, 4 '-two isocyanato-dicyclohexyl methyl hydride, tetramethylene diisocyanate, methyl pentamethylene diisocyanate, ten dimethylene diisocyanates, 1, 4-cyclohexyl diisocyanate, 4, 4 '-two isocyanato-dicyclohexyl propane-(2, 2), 1, 4-bis-isocyanato-benzene, 2, 4-bis-isocyanato-toluene, 2, 6-bis-isocyanato-toluene, two isocyanato-ditans, tetramethyl xylylen vulcabond, p-xylyl diisocyanate, more than one compounds in p-isopropylidene vulcabond.
9. the preparation method of the carbon nano tube-polyurethane mixture according to claims 1 or 2, wherein,
Described chainextender is more than one compounds be selected from ethylene glycol, propylene glycol, butyleneglycol, pentanediol and hexylene glycol.
10. the preparation method of the carbon nano tube-polyurethane mixture according to claims 1 or 2, it is relative to the urethane of the carbon nanotube compound with winding arrangement, has the electroconductibility (S/cm) of increase by 10 ~ 10000 times.
The preparation method of 11. carbon nano tube-polyurethane mixtures according to claims 1 or 2, it has the tensile strength (kgf/cm of increase by 10 ~ 100% relative to the urethane of the carbon nanotube compound with winding arrangement
2).
The preparation method of 12. carbon nano tube-polyurethane mixtures according to claims 1 or 2, it is compared relative to the urethane of the carbon nanotube compound with winding arrangement, has the unit elongation (%) of increase by 50 ~ 400%.
13. 1 kinds of carbon nano tube-polyurethane mixtures, it is by preparing according to claim 1 or claim 2.
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| US11744924B2 (en) | 2017-05-15 | 2023-09-05 | National Research Council Of Canada | Stretchable nanocomposite skin material and related structures |
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| JP6890799B2 (en) * | 2017-09-22 | 2021-06-18 | 日立Astemo株式会社 | Polyurethane composite material and method for manufacturing polyurethane composite material |
| KR102028959B1 (en) * | 2017-10-30 | 2019-10-07 | 금호석유화학 주식회사 | An adhesive composition having electic conductivity, a plastic member comprising the same, and a method for manufacturing the same |
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