CN112111145B - Conductive TPU film and preparation method thereof - Google Patents
Conductive TPU film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a conductive TPU film and a preparation method thereof. The conductive TPU film comprises the following components in parts by weight: 70-90 parts of TPU, 5-15 parts of composite conductive agent, 1-10 parts of dispersant and 1-5 parts of antioxidant; the composite conductive agent is a mixture of a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene. The preparation method has simple process, and the prepared conductive TPU film has excellent conductivity and mechanical property.
Description
Technical Field
The invention relates to the technical field of TPU materials, in particular to a conductive TPU film and a preparation method thereof.
Background
TPU (thermoplastic polyurethanes), thermoplastic polyurethane elastomer rubber, is a novel organic polymer synthetic material, can replace rubber or soft polyvinyl chloride material, has good wear resistance and rebound resilience superior to common polyurethane, has aging resistance superior to rubber, can be said to be the most ideal material for replacing PVC and PU, and is internationally called as a novel polymer material. The molecular structure of the polyurethane elastomer is formed by alternately forming a rigid block obtained by reacting diisocyanate and a chain extender and a flexible chain segment obtained by reacting diisocyanate and macromolecular polyol. The TPU has excellent high-tension, toughness and aging resistance, and is widely applied to the aspects of medical treatment and health, electronic and electric appliances, sports goods and the like.
CN107141770A discloses an electrostrictive composite material and a preparation method and application thereof, the electrostrictive composite material is prepared by 50-60% of TPU particles, 10-20% of carbon nano tubes, 20-30% of nano barium titanate, 1-5% of nano silver particles, 1-10% of nano cellulose and 5-20% of glass fibers, all components are mutually matched and have synergistic action, so that the electrostrictive rate can reach 22-24.5%, the electrostrictive composite material can be applied to the field of functional materials, and the electrostrictive composite material has good application prospect. The electrostriction of the composite material prepared by the method is improved, but the balance between the mechanical property and the electrical conductivity is poor.
CN105885390A discloses an anti-slip and anti-static TPU film and a preparation method thereof, the anti-slip and anti-static TPU film is prepared by 70-90 parts by weight of TPU particles, 20-40 parts by weight of epoxy resin, 10-15 parts by weight of polycarbodiimide, 10-20 parts by weight of nylon fibers, 20-30 parts by weight of conductive carbon fibers, 10-20 parts by weight of glass fibers and 1-5 parts by weight of antioxidant, the surface resistivity of the TPU film is 5.2 multiplied by 105-7.5×105Omega, good antistatic performance, a slip-resistant friction coefficient of 0.6-0.8, and good slip-resistant performance. In addition, the TPU film prepared by the invention has the advantages of elastic modulus of 38-42MPa, elongation at break of 550.52-628.25%, tensile stress at break of 58.5-65.7MPa, good mechanical properties, and yet the conductivity of the TPU film needs to be further improved.
Therefore, it is necessary to develop a conductive TPU film having both excellent conductive and mechanical properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a conductive TPU film and a preparation method thereof, and the prepared conductive TPU film has excellent conductive performance and mechanical property.
One of the objectives of the present invention is to provide a conductive TPU film, which adopts the following technical scheme:
a conductive TPU thin film comprises the following components in parts by weight:
the composite conductive agent is a mixture of a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene.
According to the conductive TPU film, the TPU is modified by adopting the composite conductive agent, and the conductive TPU film is matched with the dispersant and the antioxidant for use, so that the prepared TPU film has excellent conductive performance and mechanical property; the composite conductive agent is a mixture of a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene, the carboxylated carbon nanotube has active functional groups such as-COOH, -OH and the like, can form intermolecular hydrogen bonds with a TPU polymer matrix, enhances the acting force with the TPU polymer matrix, and is beneficial to the construction of a conductive network structure and the improvement of mechanical properties; the rare earth metal-doped 1-naphthoic acid modified graphene enables graphene with a plurality of carboxyl groups on the surface to have higher conductive activity, a more stable conductive network is formed, and the rare earth metal-doped 1-naphthoic acid modified graphene and the carboxylated carbon nanotube act synergistically, so that the TPU film has better conductive performance and mechanical properties.
The mass ratio of the carboxylated carbon nanotubes to the rare earth metal doped 1-naphthoic acid modified graphene is (5-10): 1-3, for example, 5:1, 5:2, 5:3, 6:1, 6:2, 6:3, 7:1, 7:2, 7:3, 8:1, 8:2, 8:3, 9:1, 9:2, 9:3, 10:1, 10:2 or 10: 3. The selection of the mass ratio range can balance the conductivity and the mechanical property, the use amount is too small, the good conductivity improvement effect cannot be achieved, and the mechanical property of the film can be reduced by too much use amount, so that the mass ratio of the carboxylated carbon nanotube to the rare earth metal doped 1-naphthoic acid modified graphene needs to be reasonably controlled.
Wherein the TPU is polyester type TPU or polyether type TPU, and the hardness is Shore A60-Shore D80.
The rare earth metal in the rare earth metal doped 1-naphthoic acid modified graphene is divalent rare earth metal.
Preferably, the divalent rare earth metal is any one of europium, ytterbium or samarium or a mixture of at least two of the europium, ytterbium or samarium.
The mass of the rare earth metal accounts for 3-8% of the mass of the rare earth metal-doped 1-naphthoic acid modified graphene, for example, the mass of the rare earth metal accounts for 3%, 4%, 5%, 6%, 7%, 8%, or the like of the rare earth metal-doped 1-naphthoic acid modified graphene.
The carboxylated carbon nanotube is any one or a mixture of at least two of a carboxylated single-wall carbon nanotube, a carboxylated double-wall carbon nanotube or a carboxylated multi-wall carbon nanotube.
The dispersing agent is any one or a mixture of at least two of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate or sodium carboxymethyl cellulose. Typical but non-limiting combinations of such mixtures are mixtures of polyvinylpyrrolidone, sodium dodecylbenzenesulfonate, mixtures of polyvinylpyrrolidone, sodium carboxymethylcellulose, mixtures of sodium dodecylbenzenesulfonate, sodium carboxymethylcellulose.
The antioxidant is one or a mixture of at least two of antioxidant 1010, antioxidant 264 or antioxidant TNP.
Another object of the present invention is to provide a method for preparing a conductive TPU film according to the first object, comprising the steps of:
1) preparing a composite conductive agent by using a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene as raw materials;
2) respectively drying the TPU, the dispersant, the antioxidant and the composite conductive agent obtained in the step 1), uniformly mixing according to the proportion, and extruding to obtain the conductive TPU film.
In the step 1), the preparation method of the composite conductive agent comprises the following steps:
a) mixing divalent rare earth metal ions, an organic solvent and 1-naphthoic acid modified graphene, and drying to obtain the rare earth metal doped 1-naphthoic acid modified graphene; wherein the mass percentage of the rare earth metal in the rare earth metal-doped 1-naphthoic acid modified graphene is 3-8%;
b) mixing the carboxylated carbon nanotube with the rare earth metal doped 1-naphthoic acid modified graphene according to the mass ratio of (5-10) to (1-3), and drying to obtain the composite conductive agent.
Preferably, in step a), the organic solvent is ethanol.
Preferably, in step b), the drying temperature is 80-100 ℃, for example, the drying temperature is 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃ or 100 ℃ and the like.
The 1-naphthoic acid modified graphene is prepared by the following method: dissolving 1-naphthoic acid in absolute ethyl alcohol according to a ratio to obtain a 1-naphthoic acid ethanol solution, then adding graphene into the 1-naphthoic acid ethanol solution, uniformly stirring at normal temperature, and filtering to obtain non-covalent bond modified graphene, namely the 1-naphthoic acid modified graphene.
Preferably, the concentration of 1-naphthoic acid in the 1-naphthoic acid ethanol solution is 1-10g/L, for example, the concentration of 1-naphthoic acid in the 1-naphthoic acid ethanol solution is 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, or 10 g/L.
Preferably, the mass ratio of the graphene to the 1-naphthoic acid is (1-10):10, for example, the mass ratio of the graphene to the 1-naphthoic acid is 1:10, 2:10, 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, or 1:1, and the like.
Compared with the prior art, the invention has the beneficial effects that:
according to the conductive TPU film, the TPU is modified by adopting the composite conductive agent, and the dispersing agent and the antioxidant are matched for use, so that the prepared TPU film has excellent conductive performance and mechanical property. Specifically, the conductive TPU film prepared by the invention has good surface resistivity of 5 multiplied by 10 and good property for people2-6×103Meanwhile, the composite material has higher mechanical property, the tensile strength is 65-75MPa, and the elongation at break is 310-380%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
Example 1
The conductive TPU film of this example comprises the following components in parts by weight:
the composite conductive agent is a mixture of a carboxylated single-walled carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene, the mass ratio of the carboxylated single-walled carbon nanotube to the rare earth metal doped 1-naphthoic acid modified graphene is 5:3, and the mass percentage of the rare earth metal in the rare earth metal doped 1-naphthoic acid modified graphene is 4%.
The preparation method of the composite conductive agent comprises the following steps:
a) mixing divalent rare earth metal europium ions, ethanol and 1-naphthoic acid modified graphene, and drying to obtain rare earth metal doped 1-naphthoic acid modified graphene; wherein the mass of the rare earth metal accounts for 4% of the mass of the rare earth metal-doped 1-naphthoic acid modified graphene;
b) and mixing the carboxylated carbon nanotube with the rare earth metal doped 1-naphthoic acid modified graphene according to the mass ratio of 5:3, and drying to obtain the composite conductive agent.
Wherein the TPU is the TPU with hardness of Shore A60, the dispersant is sodium dodecyl benzene sulfonate, and the antioxidant is antioxidant 1010.
The preparation method of the conductive TPU thin film of this embodiment comprises the following steps:
1) preparing a composite conductive agent by taking a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene as raw materials according to the proportion; the 1-naphthoic acid modified graphene is prepared by the following method: dissolving 1-naphthoic acid in absolute ethyl alcohol according to a ratio to obtain a 1-naphthoic acid ethanol solution with the concentration of 5g/L, then adding graphene into the 1-naphthoic acid ethanol solution, wherein the mass ratio of the graphene to the 1-naphthoic acid is 3:10, uniformly stirring at normal temperature, and filtering to obtain non-covalent bond modified graphene, namely 1-naphthoic acid modified graphene;
2) respectively drying the TPU, the dispersant, the antioxidant and the composite conductive agent obtained in the step 1) at 90 ℃, uniformly mixing according to the proportion, and extruding to obtain the conductive TPU film.
Example 2
The present example is different from example 1 only in that the mass ratio of the carboxylated single-walled carbon nanotubes to the rare earth metal europium-doped 1-naphthoic acid modified graphene is 5:1, and the rest is the same as example 1.
Example 3
The present example is different from example 1 only in that the mass ratio of the carboxylated single-walled carbon nanotubes to the rare earth metal europium-doped 1-naphthoic acid modified graphene is 10:1, and the rest is the same as example 1.
Example 4
The conductive TPU film of this example comprises the following components in parts by weight:
the composite conductive agent is a mixture of a carboxylated single-walled carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene, the mass ratio of the carboxylated single-walled carbon nanotube to the rare earth metal doped 1-naphthoic acid modified graphene is 5:3, and the mass percentage of the rare earth metal in the rare earth metal doped 1-naphthoic acid modified graphene is 4%.
The preparation method of the composite conductive agent comprises the following steps:
a) mixing divalent rare earth metal europium ions, ethanol and 1-naphthoic acid modified graphene, and drying to obtain rare earth metal doped 1-naphthoic acid modified graphene; wherein the mass of the rare earth metal accounts for 4% of the mass of the rare earth metal-doped 1-naphthoic acid modified graphene;
b) and mixing the carboxylated carbon nanotube with the rare earth metal doped 1-naphthoic acid modified graphene according to the mass ratio of 5:3, and drying to obtain the composite conductive agent.
Wherein the TPU is the TPU with hardness of Shore A60, the dispersant is sodium dodecyl benzene sulfonate, and the antioxidant is antioxidant 1010.
The preparation method of the conductive TPU thin film of this embodiment comprises the following steps:
1) preparing a composite conductive agent by taking a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene as raw materials according to the proportion; the 1-naphthoic acid modified graphene is prepared by the following method: dissolving 1-naphthoic acid in absolute ethyl alcohol according to a ratio to obtain a 1-naphthoic acid ethanol solution with the concentration of 5g/L, then adding graphene into the 1-naphthoic acid ethanol solution, wherein the mass ratio of the graphene to the 1-naphthoic acid is 3:10, uniformly stirring at normal temperature, and filtering to obtain non-covalent bond modified graphene, namely 1-naphthoic acid modified graphene;
2) respectively drying the TPU, the dispersant, the antioxidant and the composite conductive agent obtained in the step 1) at 90 ℃, uniformly mixing according to the proportion, and extruding to obtain the conductive TPU film.
Example 5
The conductive TPU film of this example comprises the following components in parts by weight:
the composite conductive agent is a mixture of a carboxylated double-wall carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene, the mass ratio of the carboxylated double-wall carbon nanotube to the rare earth metal samarium doped 1-naphthoic acid modified graphene is 5:2, and the mass percentage of the rare earth metal in the rare earth metal doped 1-naphthoic acid modified graphene is 6%.
Wherein the TPU is a TPU with hardness of Shore A60, the dispersant is polyvinylpyrrolidone, and the antioxidant is a mixture of 2 parts of antioxidant 264 and 3 parts of antioxidant TNP.
The preparation method of the conductive TPU thin film of this embodiment comprises the following steps:
1) preparing a composite conductive agent by taking a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene as raw materials according to the proportion; the 1-naphthoic acid modified graphene is prepared by the following method: dissolving 1-naphthoic acid in absolute ethyl alcohol according to a ratio to obtain a 1-naphthoic acid ethanol solution with the concentration of 8g/L, then adding graphene into the 1-naphthoic acid ethanol solution, wherein the mass ratio of the graphene to the 1-naphthoic acid is 4:10, uniformly stirring at normal temperature, and filtering to obtain non-covalent bond modified graphene, namely the 1-naphthoic acid modified graphene.
2) Respectively drying the TPU, the dispersant, the antioxidant and the composite conductive agent obtained in the step 1) at 80 ℃, uniformly mixing according to the proportion, and extruding to obtain the conductive TPU film.
Example 6
The present example is different from example 1 in that the mass ratio of the carboxylated single-walled carbon nanotubes to the rare earth europium-doped 1-naphthoic acid-modified graphene is 1:1, and the rest is the same as example 1.
Example 7
The present example is different from example 1 in that the mass ratio of the carboxylated single-walled carbon nanotubes to the rare earth europium-doped 1-naphthoic acid-modified graphene is 15:1, and the rest is the same as example 1.
Example 8
The present embodiment is different from embodiment 1 in that the rare earth metal in the rare earth metal doped 1-naphthoic acid modified graphene is trivalent rare earth metal terbium, and the rest is the same as that in embodiment 1.
Comparative example 1
The comparative example is different from example 1 in that the conductive agent is a carboxylated carbon nanotube, and the rare earth metal-doped 1-naphthoic acid-modified graphene is not included, and the others are the same as those of example 1.
Comparative example 2
The comparative example is different from example 1 in that the conductive agent is 1-naphthoic acid modified graphene doped with rare earth metal, does not contain the carboxylated carbon nanotube, and is otherwise the same as example 1.
Comparative example 3
This comparative example differs from example 1 in that the amount of the composite conductive agent used was 1 part, and a reduced part by weight was added to the TPU to ensure that the total part by weight was unchanged.
Comparative example 4
This comparative example differs from example 1 in that the amount of composite conductive agent used was 25 parts and the added parts by weight were subtracted from the parts by weight of TPU to ensure that the total parts by weight remained unchanged.
The TPU films obtained in examples 1 to 8 and comparative examples 1 to 4 were subjected to the performance test for conductivity and mechanical properties, and the test results for surface resistivity, tensile strength and elongation at break are shown in table 1.
The surface resistivity is tested according to the standard GB/T1414-2006, and the mechanical property of the tensile strength and the elongation at break is tested according to the standard GB 13022-91.
TABLE 1
| Surface resistivity (omega) | Tensile Strength (MPa) | Elongation at Break (%) | |
| Example 1 | 6×103 | 75 | 380 |
| Example 2 | 3×103 | 68 | 361 |
| Example 3 | 1×103 | 66 | 372 |
| Example 4 | 5×102 | 65 | 310 |
| Example 5 | 4×103 | 69 | 373 |
| Example 6 | 3×104 | 51 | 269 |
| Example 7 | 6×104 | 48 | 270 |
| Example 8 | 2×105 | 52 | 268 |
| Comparative example 1 | 7×105 | 55 | 234 |
| Comparative example 2 | 4×105 | 60 | 283 |
| Comparative example 3 | 8×104 | 57 | 240 |
| Comparative example 4 | 2×102 | 48 | 180 |
According to the conductive TPU film, the TPU is modified by adopting the composite conductive agent, and the dispersing agent and the antioxidant are matched for use, so that the prepared TPU film has excellent conductive performance and mechanical property. The conductive TPU film prepared by the invention has good surface resistivity of 5 multiplied by 102-6×103Meanwhile, the composite material has higher mechanical property, the tensile strength is 65-75MPa, and the elongation at break is 310-380%.
As can be seen from Table 1, the mass ratio of the carboxylated single-walled carbon nanotubes to the rare earth metal europium-doped 1-naphthoic acid modified graphene is lower than 5:3 or higher than 10:1, and both the conductivity and the mechanical property are reduced.
Example 8 the conductivity decreased somewhat when the rare earth metal was replaced with terbium, a trivalent rare earth metal.
In comparative examples 1 and 2, the conductivity was reduced by using the carboxylated carbon nanotube alone or the rare earth metal-doped 1-naphthoic acid-modified graphene alone without using the composite conductive agent.
In comparative example 3, the amount of the composite conductive agent used was too small, and the conductivity was reduced although the mechanical properties were improved.
The composite conductive agent of comparative example 4 was used in an excessive amount, and the conductivity was improved, but the mechanical properties were affected.
The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (14)
1. A conductive TPU film, wherein the conductive TPU film comprises the following components in parts by weight:
the composite conductive agent is a mixture of a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene;
the mass ratio of the carboxylated carbon nanotubes to the rare earth metal doped 1-naphthoic acid modified graphene is (5-10) to (1-3).
2. A conductive TPU film as set forth in claim 1 wherein the rare earth metal in the rare earth metal doped 1-naphthoic acid modified graphene is a divalent rare earth metal.
3. The conductive TPU film of claim 2, wherein the rare earth metal is any one or a mixture of at least two of europium, ytterbium or samarium.
4. A conductive TPU film as set forth in claim 1 wherein the rare earth metal is present in an amount of 3 to 8% by mass based on the rare earth metal doped 1-naphthoic acid modified graphene.
5. Conductive TPU film according to claim 1, characterized in that the carboxylated carbon nanotubes are carboxylated single-walled carbon nanotubes and/or carboxylated multi-walled carbon nanotubes.
6. A conductive TPU film as set forth in claim 1 wherein the dispersant is one or a mixture of at least two of polyvinylpyrrolidone, sodium dodecylbenzenesulfonate or sodium carboxymethylcellulose.
7. The conductive TPU film of claim 1, wherein the antioxidant is one or a mixture of at least two of antioxidant 1010, antioxidant 264 and antioxidant TNP.
8. A method for preparing a conductive TPU film as set forth in any one of claims 1-7, comprising the steps of:
1) preparing a composite conductive agent by using a carboxylated carbon nanotube and rare earth metal doped 1-naphthoic acid modified graphene as raw materials;
2) respectively drying the TPU, the dispersant, the antioxidant and the composite conductive agent obtained in the step 1), uniformly mixing according to the proportion, and extruding to obtain the conductive TPU film.
9. The preparation method according to claim 8, wherein in the step 1), the preparation method of the composite conductive agent is as follows:
a) mixing divalent rare earth metal ions, an organic solvent and 1-naphthoic acid modified graphene, and drying to obtain the rare earth metal doped 1-naphthoic acid modified graphene; wherein the mass percentage of the rare earth metal in the rare earth metal-doped 1-naphthoic acid modified graphene is 3-8%;
b) mixing the carboxylated carbon nanotube with the rare earth metal doped 1-naphthoic acid modified graphene according to the mass ratio of (5-10) to (1-3), and drying to obtain the composite conductive agent.
10. The method according to claim 9, wherein the organic solvent is ethanol in step a).
11. The method according to claim 9, wherein the drying temperature in step b) is 80 to 100 ℃.
12. The preparation method according to claim 9, wherein the 1-naphthoic acid modified graphene is prepared by a method comprising the following steps: dissolving 1-naphthoic acid in absolute ethyl alcohol according to a ratio to obtain a 1-naphthoic acid ethanol solution, then adding graphene into the 1-naphthoic acid ethanol solution, uniformly stirring at normal temperature, and filtering to obtain non-covalent bond modified graphene, namely the 1-naphthoic acid modified graphene.
13. The method according to claim 12, wherein the concentration of 1-naphthoic acid in the 1-naphthoic acid ethanol solution is 1 to 10 g/L.
14. The method according to claim 12, wherein the mass ratio of the graphene to the 1-naphthoic acid is (1-10): 10.
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