CN110903633A - High-scratch-resistance TPU (thermoplastic polyurethane) film and preparation method thereof - Google Patents
High-scratch-resistance TPU (thermoplastic polyurethane) film and preparation method thereof Download PDFInfo
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2375/06—Polyurethanes from polyesters
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2375/08—Polyurethanes from polyethers
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K3/041—Carbon nanotubes
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- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
Abstract
The invention provides a high scratch-resistant TPU film which is characterized in that the preparation raw materials of the high scratch-resistant TPU film comprise the following components in parts by weight: 60-80 parts of TPU particles, 1-10 parts of scratch resistant agent, 5-20 parts of carbon nano tube, 1-10 parts of flame retardant, 5-10 parts of filler and 1-5 parts of antioxidant. According to the invention, the carbon nano tube and the anti-scraping agent are added and matched with each other, so that the TPU film with excellent mechanical strength, high wear resistance and high scraping resistance is obtained in a synergistic manner.
Description
Technical Field
The invention belongs to the technical field of composite materials, particularly relates to a TPU film and a preparation method thereof, and particularly relates to a high-scratch-resistant TPU film and a preparation method thereof.
Background
Thermoplastic Polyurethanes (TPU) are a class of elastomeric block copolymers consisting of Hard Segments (HSs) containing rigid urethane groups and Soft Segments (SSs) containing structures capable of free-switching conformations. The carbamate groups in the hard segment regions (HSs) have strong polarity, and are easy to form intramolecular hydrogen bonds, and the carbamate groups are gathered together to form hard segment micro-phase regions, and the micro-regions play the roles of physical cross-linking points and internal reinforcing agents in the whole TPU molecules at room temperature, so that excellent performances such as high modulus and high hardness are endowed to the TPU material; the soft segment regions (SSs) impart good rubber elasticity and low temperature resistance to the TPU elastomer. Based on the performance advantages, the TPU is widely applied to the fields of building materials, automobile parts, sports equipment, film materials and the like.
The research of Carbon Nanotubes (CNTs) has made great progress, especially in the preparation, structural applications, etc. carbon nanotubes have extremely high toughness, their structure with graphite and C60Similarly, the hollow cylinder is formed by concentric graphite surfaces, so that the hollow cylinder has excellent self-lubricating property and can improve the friction and wear properties of a polymer matrix.
CN105966027A discloses an environmental protection type TPU synthetic leather that is ventilative, the components and the part by weight of TPU top layer are: 30-95 parts of TPU particles, 3-25 parts of flame retardant, 2-15 parts of pigment, 0-5 parts of light stabilizer, 0-5 parts of scratch resistant agent and 0-20 parts of filler, wherein the scratch resistant agent is a silicone polymer and has low scratch and abrasion resistance, poor scratch resistance and low glossiness.
Therefore, the development of the scratch-resistant and wear-resistant TPU film which has extremely strong mechanical properties is the focus of research in the field of current materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a TPU film and a preparation method thereof, in particular to a high-scratch-resistant TPU film and a preparation method thereof, so that the TPU film has extremely strong mechanical property, scratch resistance, wear resistance and soft luster, and the production cost is greatly reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high scratch resistant TPU film, which is prepared from the following raw materials in parts by weight:
the parts by weight of the TPU granules in the present invention are from 60 to 80 parts by weight, and may be, for example, 60 parts by weight, 61 parts by weight, 63 parts by weight, 65 parts by weight, 67 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 75 parts by weight, 77 parts by weight, 79 parts by weight or 80 parts by weight.
The weight part of the scratch resistant agent in the present invention is 1 to 10 parts by weight, and may be, for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight.
The carbon nanotubes in the present invention may be used in an amount of 5 to 20 parts by weight, for example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 19 parts by weight, or 20 parts by weight.
The amount of the flame retardant in the present invention is 1 to 10 parts by weight, and may be, for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
The filler in the present invention is used in an amount of 5 to 10 parts by weight, for example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight.
The antioxidant in the present invention is used in an amount of 1 to 5 parts by weight, for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight or 5 parts by weight.
According to the invention, the carbon nano tube has unique properties such as large length-diameter ratio, low density, high mechanical, thermal and electrical properties and good self-lubricating property, the frictional wear property of the TPU film is improved by adding the carbon nano tube, the carbon nano tube has a remarkable enhancement effect on improving the mechanical property of the TPU film matrix, and after a proper amount of carbon nano tube is added, the thermal property and the mechanical property of the TPU film composite material are remarkably improved, including the macroscopic mechanical properties such as hardness, frictional wear, tensile strength, tearing resistance and the like of the TPU film.
Preferably, the TPU particles are any one or a mixture of at least two of polyester, polyether or aliphatic TPU, preferably polyester TPU particles.
Preferably, the scratch resistant agent is any one or a mixture of at least two of nano silicon dioxide, nano aluminum oxide or nano titanium dioxide.
In the invention, the characteristics of small size effect, large specific surface area, high surface energy, insufficient surface coordination and the like of the nano silicon dioxide enable the nano silicon dioxide to easily have bonding effect with oxygen in TPU, and improve the molecular bonding force; meanwhile, the material is easy to distribute in the gaps of the polymer chains, so that the strength, the toughness and the ductility of the material are greatly improved. And the quantum size and macroscopic quantum tunnel effect of the nano silicon dioxide enable the nano silicon dioxide to generate a silting and permeating effect, the nano silicon dioxide can penetrate into the vicinity of unsaturated bonds of TPU molecular chains and can react with electronic clouds of the unsaturated bonds, so that the thermal stability, the light stability and the chemical stability of the TPU are improved, and the purposes of improving the aging performance, the chemical resistance and the like of products are achieved.
The nano aluminum oxide basically does not corrode in natural environment, has good structural compatibility, has high bonding strength with TPU (thermoplastic polyurethane) particles, and has the characteristics of high strength, small friction coefficient, low wear rate and the like.
When the nano titanium dioxide is used as a scratch resistant agent, the nano titanium dioxide has the functions of reducing friction, resisting abrasion and scratch, self-cleaning, repairing the surface and the like, and has excellent characteristics of good wear resistance, chemical corrosion resistance, ultraviolet resistance and the like.
In the invention, the scratch-resistant agent and the carbon nano tube are mutually matched and synergized, so that the TPU film has stronger mechanical property, and the effects of scraping resistance, wear resistance and luster and softness of the surface of the film are improved.
Preferably, the scratch resistant agent is a mixture of nano silica and nano alumina.
Preferably, the mass ratio of the nano-silica to the nano-alumina is (0.5-3):1, and can be, for example, 0.5:1, 0.6:1, 0.8:1, 0.9:1, 1:1, 1.5:1, 2:1, 2.5:1, 3: 1.
Preferably, the scratch resistant agent is a mixture of nano aluminum oxide and nano titanium dioxide.
Preferably, the mass ratio of the nano aluminum oxide to the nano titanium dioxide is (1-4):1, and for example, the mass ratio can be 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1 and 4: 1.
Preferably, the carbon nanotubes are multi-walled carbon nanotubes.
The multi-wall carbon nano tube has large proportion of surface atomic number, has unsaturation, and can generate great acting force between two mixed phases when acting with other components, thereby having more excellent strengthening and toughening effects on TPU films.
Preferably, the multi-walled carbon nanotube has a length of 10-30 μm, and may be, for example, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 30 μm.
Preferably, the multi-walled carbon nanotubes have a diameter of 8-15 μm, and may be, for example, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm.
Preferably, the flame retardant is decabromodiphenylethane mixed micro fumed silica.
Preferably, the filler is any one or a mixture of at least two of calcium carbonate, kaolin, talcum powder, mica powder or montmorillonite, and is preferably montmorillonite.
Preferably, the antioxidant is one or a mixture of at least two of antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant TPP or antioxidant TNP.
Preferably, the method comprises the steps of:
(1) pre-drying the components;
(2) and mixing the components according to the formula amount, and extruding to obtain the high scratch-resistant TPU film.
Preferably, the drying temperature in the step (1) is 80-90 ℃;
preferably, the time of step (1) is 4-5 h;
preferably, the temperature of the extrusion in step (2) is 180-200 ℃.
Preferably, the method comprises the steps of:
(1) pre-drying the components; the drying temperature is 80-90 ℃, and the drying time is 4-5 h;
(2) the components are mixed according to the formula amount, and the high scratch-resistant TPU film is obtained by extrusion at the temperature of 180-200 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the TPU has extremely strong mechanical property by adding the carbon nano tube, the mechanical property of the TPI film is improved, the TPI film is scratch-resistant and wear-resistant and has soft luster, and the production cost is greatly reduced.
(2) In the invention, the scratch resistant agent is added, so that the strength, toughness and ductility of the high-scratch resistant TPU film are greatly improved, and the high-scratch resistant TPU film has excellent characteristics of good wear resistance, chemical corrosion resistance and the like.
(3) The carbon nano tube and the scratch resistant agent are mutually matched and cooperate to ensure that the high-scratch resistant TPU film has extremely strong mechanical property and abrasion and scratch resistant capability, the tensile strength range is 65-88.5MPa, the elongation at break range is 550-700%, the tear strength range is 65-85kN/m, the hardness range is 80-95A, and the abrasion loss is only 2-15 mg.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The high scratch-resistant TPU film is prepared from the following raw materials in parts by weight: 70 parts of Desmopan 460 polyester TPU particles, 6 parts of a mixture (mass ratio is 2:1) of nano silicon dioxide and nano aluminum oxide, 15 parts of multi-wall carbon nano tubes (length is 20 microns, diameter is 10 microns), 2 parts of decabromodiphenyl ethane mixed trace calcined silicon dioxide, 5 parts of montmorillonite and 10102 parts of antioxidant.
The method comprises the following steps:
(1) pre-drying the components; the drying temperature is 80 ℃, and the drying time is 4 hours;
(2) 70 parts of Desmopan 460TPU particles, 6 parts of a mixture (mass ratio is 2:1) of nano silicon dioxide and nano aluminum oxide, 15 parts of multi-wall carbon nano tubes (length is 20 mu m, diameter is 10 mu m), 2 parts of decabromodiphenyl ethane mixed with trace calcined silicon dioxide, 5 parts of montmorillonite and 10102 parts of antioxidant are mixed, and the mixture is extruded at 200 ℃ to obtain the high scratch-resistant TPU film.
Example 2
The difference is only that the mass ratio of the mixture of the nano silicon dioxide and the nano aluminum oxide is 5:1, and the contents of other components and the preparation method are not changed as in example 1.
Example 3
The difference from example 1 is that the anti-scratch agent is nano silicon dioxide, does not contain nano alumina, and the contents of other components and the preparation method are not changed.
Example 4
The high scratch-resistant TPU film is prepared from the following raw materials in parts by weight: 66 parts of Desmopan 385E polyester TPU particles, 8 parts of a mixture (mass ratio is 3:1) of nano alumina and nano titanium dioxide, 16 parts of multi-wall carbon nano tubes (the length is 10 mu m, and the diameter is 8 mu m), 3 parts of decabromodiphenyl ethane mixed trace calcined silicon dioxide, 6 parts of montmorillonite and 10761 parts of antioxidant.
The method comprises the following steps:
(1) pre-drying the components; the drying temperature is 90 ℃, and the drying time is 5 hours;
(2) 66 parts of Desmopan 385E TPU particles, 8 parts of a mixture of nano-alumina and nano-titanium dioxide (the mass ratio is 3:1), 16 parts of multi-wall carbon nano-tubes (the length is 10 mu m, and the diameter is 8 mu m), 3 parts of decabromodiphenyl ethane mixed with trace calcined silica, 6 parts of montmorillonite and 10761 parts of antioxidant are mixed, and the mixture is extruded at 180 ℃ to obtain the high scratch-resistant TPU film.
Example 5
The difference is that the mass ratio of the mixture of the nano alumina and the nano titanium dioxide is 0.5:1, the nano titanium dioxide is not contained, and the contents of other components and the preparation method are not changed as in example 3.
Example 6
The difference from example 3 is only that the anti-scraping agent is nano alumina, nano titanium dioxide is not contained, and the contents of other components and the preparation method are not changed.
Example 7
The high scratch-resistant TPU film is prepared from the following raw materials in parts by weight: 70 parts of Estane 58252 polyether TPU particles, 10 parts of a mixture (mass ratio is 4:1) of nano silicon dioxide and nano aluminum oxide, 10 parts of single-walled carbon nanotubes (with the length of 20 mu m and the diameter of 1 mu m), 2 parts of decabromodiphenylethane mixed trace calcined silicon dioxide, 5 parts of talcum powder and 10103 parts of antioxidant.
The method comprises the following steps:
(1) pre-drying the components; the drying temperature is 85 ℃, and the drying time is 4 hours;
(2) 70 parts of Estane 58252 polyether TPU particles, 10 parts of a mixture (mass ratio is 4:1) of nano silicon dioxide and nano aluminum oxide, 10 parts of single-walled carbon nanotubes (with the length of 20 mu m and the diameter of 1 mu m), 2 parts of decabromodiphenylethane mixed with trace calcined silicon dioxide, 5 parts of talcum powder and 10103 parts of antioxidant are mixed, and the mixture is extruded at 200 ℃ to obtain the high-scratch-resistant TPU film.
Example 8
The high scratch-resistant TPU film is prepared from the following raw materials in parts by weight: 80 parts of ALRG2000 aliphatic TPU particles, 1 part of a mixture (mass ratio is 2:1) of nano silicon dioxide and nano titanium dioxide, 5 parts of multi-walled carbon nanotubes (with the length of 30 mu m and the diameter of 30 mu m), 5 parts of decabromodiphenylethane mixed trace calcined silicon dioxide, 8 parts of calcium carbonate and 1 part of antioxidant TPP.
The method comprises the following steps:
(1) pre-drying the components; the drying temperature is 80 ℃, and the drying time is 4 hours;
(2) 80 parts of ALR G2000 aliphatic TPU particles, 6 parts of a mixture (mass ratio is 2:1) of nano silicon dioxide and nano titanium dioxide, 6 parts of multi-walled carbon nanotubes (with the length of 30 mu m and the diameter of 30 mu m), 1 part of decabromodiphenylethane mixed trace calcined silicon dioxide, 5 parts of calcium carbonate and 2 parts of antioxidant TPP are mixed, and the mixture is extruded at 180 ℃ to obtain the high scratch-resistant TPU film.
Example 9
The high scratch-resistant TPU film is prepared from the following raw materials in parts by weight: 60 parts of TPUAC85A aliphatic TPU particles, 10 parts of nano-silica, 20 parts of single-walled carbon nanotubes (5 microns in length and 2 microns in diameter), 4 parts of decabromodiphenylethane mixed trace fumed silica, 5 parts of calcium carbonate and 1 part of antioxidant TPP.
The method comprises the following steps:
(1) pre-drying the components; the drying temperature is 90 ℃, and the drying time is 5 hours;
(2) 60 parts of TPU AC85A aliphatic TPU particles, 10 parts of nano-silica, 20 parts of single-walled carbon nanotubes (5 microns in length and 2 microns in diameter), 4 parts of decabromodiphenylethane mixed trace fumed silica, 5 parts of calcium carbonate and 1 part of antioxidant TPP are mixed, and the mixture is extruded at 200 ℃ to obtain the high-scratch-resistant TPU film.
Comparative example 1
The difference from example 1 is that the scratch resistant agent is a mixture of 21 parts by weight of nano silica and nano alumina, and the scratch resistant agent does not contain carbon nanotubes, and the contents of other components and the preparation method are not changed.
Comparative example 2
The difference is only that the weight part of the multi-wall carbon nano tube is 21 parts, the anti-scraping agent is not contained, and the contents of other components and the preparation method are not changed as in example 1.
Comparative example 3
The difference from example 1 is that the multi-walled carbon nanotubes are replaced by graphene, and the contents of other components and the preparation method are not changed.
Comparative example 4
The difference is that the mixture of the scratch resistant nano silicon dioxide and the nano aluminum oxide is replaced by the scratch resistant poly (methyl phenyl siloxane) with the same content of other components and preparation method as the example 1.
Comparative example 5
The difference from example 3 is that the weight portion of the mixture of the anti-scraping agent nano aluminum oxide and the nano titanium dioxide is 22 weight portions, the carbon nano tube is not contained, and the contents of other components and the preparation method are not changed.
Performance testing
The TPU films of examples 1 to 7 and comparative examples 1 to 5 were subjected to a performance test, the tensile strength was tested according to GB/T1040.3-2006, the elongation at break was tested according to GB/T1040.1-2006, the tear strength was tested according to GBT529-2008, the hardness was tested according to GB/T531.1, the abrasion loss was tested according to GB/T9867, the scratch resistance test was tested according to Ford standard FLTM BN 108-13, the load was 2N, the scratch resistance was judged by judging the degree of whitening of the surface of the scratched test piece, the lower the degree of whitening, the better the scratch resistance of the material was indicated, and the results of the performance tests are shown in Table 1:
TABLE 1
As can be seen from the data in Table 1, the samples of examples 1-7 have tensile strength ranging from 68 MPa to 90MPa, elongation at break ranging from 520 ℃ to 700%, tear strength ranging from 65 kN/m to 85kN/m and hardness ranging from 80A to 95A, and the high scratch-resistant TPU film has excellent macroscopic mechanical properties and various mechanical strengths; the abrasion loss of the samples of examples 1 to 7 was only 2 to 15mg, and the samples of examples 1 to 7 were judged to have no blushing or slight blushing in the scratch resistance by judging the blushing degree of the surface of the scratched test piece, indicating that the high scratch resistant TPU film described herein has excellent abrasion and scratch resistance.
As can be seen from comparative examples 1, 2 and 5, when any one of the carbon nanotubes or the scratch resistance agent is absent, the mechanical strengths of the TPU film are remarkably reduced; while comparative examples 3-4 replace the carbon nanotubes and scratch resistance described herein with similar compositions, while the properties are improved compared to the TPU films of comparative examples 1-2, the mechanical strength is still much lower compared to the TPU films described herein, which illustrates that the carbon nanotubes and scratch resistance described herein cooperate with each other to synergistically enhance the mechanical strength, abrasion and scratch resistance of the TPU films described herein.
The applicant states that the invention is illustrated by the above examples of the highly scratch resistant TPU film of the invention, but the invention is not limited to the above examples, i.e. it does not mean that the invention must be practiced in reliance on the above examples. 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.
Claims (10)
1. The high scratch-resistant TPU film is characterized in that the preparation raw material of the high scratch-resistant TPU film comprises the following components in parts by weight:
2. the high scratch resistant TPU film of claim 1 where the TPU particles are any one or a mixture of at least two of polyester, polyether or aliphatic TPU.
3. The high scratch resistant TPU film of claim 1 or 2, wherein the scratch resistant agent is any one or a mixture of at least two of nano silica, nano alumina or nano titania;
preferably, the scratch resistant agent is a mixture of nano silicon dioxide and nano aluminum oxide;
preferably, the mass ratio of the nano silicon dioxide to the nano aluminum oxide is (0.5-3) to 1;
preferably, the scratch resistant agent is a mixture of nano aluminum oxide and nano titanium dioxide;
preferably, the mass ratio of the nano aluminum oxide to the nano titanium dioxide is (1-4): 1.
4. The high scratch resistant TPU film of any of claims 1 to 3, wherein the carbon nanotubes are multi-walled carbon nanotubes;
preferably, the multi-walled carbon nanotube is 10-30 μm in length;
preferably, the diameter of the multi-walled carbon nanotube is 8-15 μm.
5. The high scratch resistant TPU film of any of claims 1 to 4 wherein the flame retardant is decabromodiphenylethane mixed with a minor amount of fumed silica.
6. The high scratch resistant TPU film of any one of claims 1 to 5, wherein the filler is any one or a mixture of at least two of calcium carbonate, kaolin, talc, mica powder or montmorillonite, preferably montmorillonite.
7. The high scratch resistant TPU film of any one of claims 1 to 6, wherein the antioxidant is any one or a mixture of at least two of antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant TPP or antioxidant TNP.
8. The method for preparing a high scratch resistant TPU film as claimed in any of claims 1 to 7, characterized in that the method comprises the following steps:
(1) pre-drying the components;
(2) and mixing the components according to the formula amount, and extruding to obtain the high scratch-resistant TPU film.
9. The method according to claim 8, wherein the drying temperature in the step (1) is 80 to 90 ℃;
preferably, the time of step (1) is 4-5 h;
preferably, the temperature of the extrusion in step (2) is 180-200 ℃.
10. The method for preparing according to claim 8 or 9, characterized in that it comprises the following steps:
(1) pre-drying the components; the drying temperature is 80-90 ℃, and the drying time is 4-5 h;
(2) the components are mixed according to the formula amount, and the high scratch-resistant TPU film is obtained by extrusion at the temperature of 180-200 ℃.
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| CN201911195348.XA CN110903633A (en) | 2019-11-28 | 2019-11-28 | High-scratch-resistance TPU (thermoplastic polyurethane) film and preparation method thereof |
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| CN113307995A (en) * | 2021-04-30 | 2021-08-27 | 苏州市雄林新材料科技有限公司 | Temperature-resistant thermoplastic polyurethane film and preparation method thereof |
| CN113881217A (en) * | 2021-10-08 | 2022-01-04 | 广州敬信高聚物科技有限公司 | Scratch-resistant flame-retardant thermoplastic polyurethane material and preparation method and application thereof |
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