CN113307995A - Temperature-resistant thermoplastic polyurethane film and preparation method thereof - Google Patents
Temperature-resistant thermoplastic polyurethane film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a temperature-resistant thermoplastic polyurethane film and a preparation method thereof, wherein the temperature-resistant thermoplastic polyurethane film is prepared from the combination of thermoplastic polyurethane, graphene, nano silicon dioxide, mica sheets and an anti-UV agent; the temperature-resistant thermoplastic polyurethane film is prepared from graphene in a specific part and mica sheets, so that the temperature resistance of the finally obtained polyurethane film is effectively improved, the nano-silica in a specific part is further added, the temperature resistance of the polyurethane film is further improved, the mechanical property of the polyurethane film is improved, and the heat-resistant thermoplastic polyurethane film has important research value.
Description
Technical Field
The invention belongs to the technical field of polyurethane films, and particularly relates to a temperature-resistant thermoplastic polyurethane film and a preparation method thereof.
Background
The polyurethane elastomer is a high polymer material polymerized by taking diisocyanate and oligomer polyol as basic raw materials, has the advantages of good mechanical property, wear resistance, oil resistance, tearing resistance, aging corrosion resistance, ray radiation resistance, excellent bonding property and the like, but the use temperature of the polyurethane elastomer can not exceed 80 ℃, the polyurethane elastomer can be softened and deformed when used at the temperature of more than 100 ℃, the mechanical property is obviously weakened, the short-term use temperature can not exceed 120 ℃, and the application range of the polyurethane elastomer is severely limited.
Therefore, although researchers in many research institutes have studied the heat resistance and temperature resistance of polyurethane elastomers, the polyurethane elastomers have a very complicated structure and many factors affecting the heat deformation resistance, and thus, many research directions have been made on improving the heat resistance and temperature resistance. CN111454564A discloses a high temperature resistant TPU film and a preparation process thereof, wherein the TPU film comprises the following components in parts by weight: 90-100 parts of 90A raw material particles and 5-10 parts of hydroxyl spherical glass bead master batch, wherein the preparation process comprises the following steps: respectively putting the 90A raw material particles and the hydroxyl spherical glass bead master batch in parts by weight into a stirrer and uniformly stirring; putting the uniformly mixed mixture of the 90A raw material particles and the hydroxyl spherical glass bead master batches into a drying dehumidifier for drying and dehumidifying, and taking out after drying and dehumidifying are completed for 2-3 h; putting the dried and dehumidified mixture into a double-screw extruder, plasticizing and extruding the mixture after a period of time, and cutting the mixture after cooling the mixture by cold water to obtain TPU film particles; and drying the obtained TPU film particles, putting the dried TPU film particles into a casting machine, carrying out casting process treatment, and carrying out roll forming by using a cooling roll to obtain the high-temperature-resistant TPU film. CN107189409A discloses a high temperature resistant TPU film and a preparation method thereof, the TPU film is prepared by using 60-70 parts by weight of polyester type TPU particles, 5-10 parts by weight of glass fibers, 10-20 parts by weight of carbon nanofibers, 10-20 parts by weight of silicon dioxide, 10-15 parts by weight of white carbon black, 0.5-0.6 part by weight of antioxidant and 0.1-0.3 part by weight of dibutyltin dioctoate, and the high temperature resistance of the TPU film is 93-96% through the cooperation and synergistic effect among the components, so that the TPU film has a good application prospect. CN105038187A discloses a high temperature resistant TPU film, which takes TPU particles as raw materials, and also comprises a leveling agent, white carbon black, soybean protein, thiourea, benzyl silicone oil and an antioxidant, and the components are respectively as follows by weight: 70-80 parts of TPU particles, 1-3 parts of a flatting agent, 5-8 parts of white carbon black, 10-12 parts of soybean protein, 1-3 parts of thiourea, 0.8-1.2 parts of benzyl silicone oil and 1-5 parts of an antioxidant. The beneficial effects of the invention are: the additive added into the TPU particles can effectively enhance the high-temperature resistance of the film, the proportion is scientific and reasonable, and the performance of the film is effectively improved by adding the soybean protein and the benzyl silicone oil.
However, the polyurethane film obtained in the above patent has poor mechanical properties and still has to be improved in temperature resistance.
Therefore, the development of a thermoplastic polyurethane film with excellent mechanical properties and temperature resistance is a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a temperature-resistant thermoplastic polyurethane film and a preparation method thereof; the material of the temperature-resistant thermoplastic polyurethane film comprises specific parts of thermoplastic polyurethane, and specific parts of graphene, nano-silica and mica sheets are matched, wherein the graphene and the mica sheets are of two-dimensional sheet structures, and have a heat insulation effect when being filled into a polyurethane matrix, so that the heat resistance of the finally obtained polyurethane film is effectively improved, and the specific parts of nano-silica are further added, so that the mechanical property of the polyurethane film is obviously improved, and the heat resistance of the polyurethane film is further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a temperature-resistant thermoplastic polyurethane film, which comprises the following components in parts by weight:
the thermoplastic polyurethane comprises 81, 82, 83, 84, 85, 86, 87, 88 or 89 parts by weight, and the specific values therebetween are not exhaustive of the specific values included in the ranges, limited to space and for the sake of brevity.
The graphene may be 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, or 9.5 parts by weight, and specific values therebetween, which are limited by space and for the sake of brevity, are not exhaustive, and are not included in the scope of the present invention.
The nanosilica may be 7.2 parts by weight, 7.4 parts by weight, 7.6 parts by weight, 7.8 parts by weight, 8 parts by weight, 8.2 parts by weight, 8.4 parts by weight, 8.6 parts by weight, or 8.8 parts by weight, and specific values therebetween, not to limit the disclosure and for brevity, the specific values included in the ranges are not exhaustive.
The mica sheet may be 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, or 9.5 parts by weight, and specific points therebetween, not to limit the disclosure and for brevity, the invention is not exhaustive of the specific points included in the ranges.
The UV resistant agent may be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, or 9.5 parts by weight, and specific point values therebetween are limited in space and for brevity, and the present invention is not exhaustive of the specific point values included in the range.
The temperature-resistant thermoplastic polyurethane film provided by the invention comprises specific parts of thermoplastic polyurethane, and specific parts of graphene, nano-silica and mica sheets are matched, and the two-dimensional sheet structure of the graphene and the mica sheets is filled in a polyurethane matrix to play a heat insulation role, so that the heat resistance of the finally obtained polyurethane film is effectively improved, the specific parts of nano-silica is further added, and the graphene and the mica sheets are matched, so that the mechanical property of the polyurethane film is obviously improved, and the heat resistance of the polyurethane film is further improved.
Preferably, the preparation raw material of the thermoplastic polyurethane comprises the following components in parts by weight:
the aromatic diisocyanate may be 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, or 59 parts by weight, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and clarity.
The polytetrahydrofuran ether glycol can be 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight, or 14.5 parts by weight, and the specific values therebetween are not exhaustive and are not included in the scope of the invention for reasons of brevity.
The hydroxyl terminated polydimethylsiloxane may be 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight, or 14.5 parts by weight, and the specific values therebetween are not exhaustive and are included in the scope of the present invention for brevity.
The catalyst may be present in an amount of 2.5, 3, 3.5, 4, or 4.5 parts by weight, and the particular points therebetween are not exhaustive of the invention for reasons of brevity and clarity.
The chain extender may be 11, 12, 13, 14, 15, 16, 17, 18 or 19 parts by weight, and the specific points therebetween are not exhaustive of the invention for the sake of brevity and clarity and are not intended to be included within the stated ranges.
As a preferred technical scheme of the invention, in the material of the temperature-resistant thermoplastic polyurethane film provided by the invention, the raw materials for preparing the thermoplastic polyurethane adopt aromatic diisocyanate, polytetrahydrofuran ether glycol and hydroxyl-terminated polydimethylsiloxane as main synthetic raw materials, and polytetrahydrofuran ether glycol and hydroxyl-terminated polydimethylsiloxane as mixed soft sections of the thermoplastic polyurethane material, so that the heat resistance of the obtained thermoplastic polyurethane is effectively improved, and the temperature resistance of the finally obtained polyurethane film is further improved.
Preferably, the aromatic diisocyanate comprises 1, 5-naphthalene diisocyanate.
As a preferred technical scheme of the invention, the aromatic diisocyanate selects 1, 5-naphthalene diisocyanate, the 1, 5-naphthalene diisocyanate has a naphthalene ring structure and higher molecular chain regularity, and further polyurethane synthesized by taking the aromatic diisocyanate as a hard segment has higher melting point and better temperature resistance.
Preferably, the catalyst comprises stannous isooctanoate and/or dibutyltin dilaurate.
Preferably, the chain extender comprises any one of 4,4 ' -xylene methane-5-maleimide, 3 ' -dichloro-4, 4 ' -diphenylmethane diamine or hydroquinone bis-hydroxyethyl ether or a combination of at least two thereof; further preferred is 4,4 ' -xylylene-5-maleimide and/or 3,3 ' -dichloro-4, 4 ' -diphenylmethanediamine.
As a preferred technical scheme, 4 '-xylene methane-5-maleimide and/or 3, 3' -dichloro-4, 4 '-diphenylmethane diamine are/is adopted as a chain extender, and a 4, 4' -xylene methane-5-maleimide aromatic ring structure is introduced, so that a rigid chain segment in the synthesized polyurethane is relatively improved, and the thermal stability of the polyurethane material is obviously improved.
Preferably, the preparation raw materials of the thermoplastic polyurethane also comprise a cocatalyst and/or a crosslinking agent.
As a preferred technical scheme, the preparation raw material of the thermoplastic polyurethane provided by the invention also comprises a cocatalyst and a crosslinking agent, wherein the cocatalyst can absorb carbon dioxide released by the reaction of the obtained NCO group and water, so that the formation of a crosslinking bond is facilitated, and the crosslinking agent is added for matching, so that the mechanical property and the thermal stability of the finally obtained polyurethane material are improved.
Preferably, the amount of the co-catalyst in the raw materials for preparing the thermoplastic polyurethane is 1 to 5 parts by weight, for example, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight, and specific values therebetween are not exhaustive, and for the sake of brevity, the invention is not limited to the specific values included in the ranges.
Preferably, the co-catalyst comprises propylene diamine.
Preferably, the amount of the cross-linking agent in the raw material for preparing the thermoplastic polyurethane is 1 to 5 parts by weight, for example, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight, and specific values therebetween are not exhaustive, and for the sake of brevity, the invention is not limited to the specific values included in the ranges.
Preferably, the cross-linking agent comprises a triol.
Preferably, the thermoplastic polyurethane is prepared by a process comprising the steps of:
(A1) reacting aromatic diisocyanate, polytetrahydrofuran ether glycol, hydroxyl-terminated polydimethylsiloxane, a catalyst and an optional cocatalyst to obtain a prepolymer;
(A2) and (2) reacting the prepolymer obtained in the step (1), a chain extender and an optional cross-linking agent to obtain the thermoplastic polyurethane.
Preferably, the reaction temperature in the step (a1) is 70-80 ℃, for example 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃ or 79 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time of step (a1) is 2-3 h, such as 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 2.9h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not exhaustive.
Preferably, the reaction temperature in the step (a2) is 40 to 60 ℃, for example, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ or 58 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time of step (a2) is 6-12 h, such as 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h or 11.5h, and the specific values therebetween are not exhaustive, and for brevity and clarity.
Preferably, the material of the temperature-resistant thermoplastic polyurethane film further comprises any one or a combination of at least two of an abrasion-resistant additive, an antioxidant, a lubricant or a pigment.
Preferably, the content of the abrasion resistant additive in the material of the temperature resistant thermoplastic polyurethane film is 1 to 5 parts by weight, such as 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight, and specific points therebetween, which are limited by space and for the sake of brevity, the present invention does not exhaustively enumerate the specific points included in the range.
Preferably, the anti-wear additive comprises any one of polytetrafluoroethylene fibers, molybdenum disulfide, graphite, or polyimide fibers, or a combination of at least two of the foregoing.
Preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
preferably, the antioxidant is contained in the material of the temperature-resistant thermoplastic polyurethane film in an amount of 1 to 5 parts by weight, for example, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight, and specific points therebetween are not exhaustive, and the invention is not limited to the specific points included in the range for brevity.
Preferably, the amount of the lubricant in the material of the temperature-resistant thermoplastic polyurethane film is 0.5 to 2 parts by weight, such as 0.7 part by weight, 0.9 part by weight, 1.1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7 parts by weight or 1.9 parts by weight, and specific values therebetween are not exhaustive, and for the sake of brevity, the invention is not limited to the specific values included in the ranges.
Preferably, the slip agent comprises any one or a combination of at least two of erucamide, oleamide, C wax, or montan wax.
Preferably, the pigment is contained in the material of the temperature-resistant thermoplastic polyurethane film in an amount of 0.5 to 2 parts by weight, for example, 0.7 part by weight, 0.9 part by weight, 1.1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7 parts by weight or 1.9 parts by weight, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and conciseness.
Preferably, the pigment includes any one of phthalocyanine red, phthalocyanine blue, phthalocyanine green, fast scarlet, macrored, macroyellow, permanent yellow, permanent violet, or azoic red or a combination of at least two thereof.
In a second aspect, the present invention provides a method for preparing the temperature-resistant thermoplastic polyurethane film according to the first aspect, wherein the method comprises: and (2) melt-extruding, cooling and stretching thermoplastic polyurethane, graphene, nano silicon dioxide, mica sheets, an anti-UV agent, an optional wear-resistant additive, an optional antioxidant, an optional lubricant and an optional pigment to obtain the temperature-resistant thermoplastic polyurethane film.
Preferably, the melt extrusion temperature is 170-200 ℃, such as 173 ℃, 176 ℃, 179 ℃, 183 ℃, 186 ℃, 189 ℃, 193 ℃, 196 ℃ or 199 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the melt extrusion pressure is 10 to 20Mpa, such as 11Mpa, 12Mpa, 13Mpa, 14Mpa, 15Mpa, 16Mpa, 17Mpa, 18Mpa or 19Mpa, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the melt extrusion is performed by a single screw extruder.
Preferably, the single screw extruder has a rotation speed of 20 to 100rpm, such as 25rpm, 30rpm, 35rpm, 40rpm, 45rpm, 50rpm, 60rpm, 70rpm, 80rpm or 90rpm, and specific values therebetween, which are not exhaustive for the invention and are included in the range for brevity.
As a preferred technical scheme, the preparation method comprises the following steps: the temperature-resistant thermoplastic polyurethane film is prepared by melt-extruding, cooling and stretching thermoplastic polyurethane, graphene, nano-silica, mica sheets, an anti-UV agent, an optional wear-resistant additive, an optional antioxidant, an optional lubricant and an optional pigment at 170-200 ℃ through a single-screw extruder with the rotating speed of 20-100 rpm.
Compared with the prior art, the invention has the following beneficial effects:
according to the temperature-resistant thermoplastic polyurethane film provided by the invention, the thermoplastic polyurethane with a specific part is added into the material, the graphene, the nano-silica and the mica sheet with a specific part are matched as the filler, the graphene and the mica sheet are of two-dimensional sheet structures, and the two-dimensional sheet structures are filled into a polyurethane matrix to have a heat insulation effect, so that the temperature resistance of the finally obtained polyurethane film is effectively improved; the nano silicon dioxide with a specific part is further added, so that the mechanical property of the polyurethane film is obviously improved, and the temperature resistance of the polyurethane film is further improved; specifically, the temperature-resistant thermoplastic polyurethane film provided by the invention has the advantages of tensile strength of 34-40 MPa, elongation of 563-589%, melting point of 148-170 ℃, and excellent mechanical property and temperature resistance.
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.
Preparation example 1
The thermoplastic polyurethane comprises the following components in parts by weight:
the preparation method of the thermoplastic polyurethane provided by the preparation example comprises the following steps:
(1) 1, 5-naphthalene diisocyanate, polytetrahydrofuran ether glycol, hydroxyl-terminated polydimethylsiloxane (CAS:70131-67-8), stannous isooctanoate, dibutyltin dilaurate and propylene diamine are reacted for 2.5 hours at the temperature of 75 ℃ to obtain a prepolymer;
(2) and (2) reacting the prepolymer obtained in the step (1), 4' -xylene methane-5-maleimide triol and at the temperature of 50 ℃ for 10 hours to obtain the thermoplastic polyurethane.
Preparation example 2
The thermoplastic polyurethane comprises the following components in parts by weight:
the preparation method of the thermoplastic polyurethane provided by the preparation example comprises the following steps:
(1) 1, 5-naphthalene diisocyanate, polytetrahydrofuran ether glycol, hydroxyl-terminated polydimethylsiloxane (CAS:70131-67-8), stannous isooctanoate, dibutyltin dilaurate and propylene diamine are reacted for 3 hours at 70 ℃ to obtain a prepolymer;
(2) and (2) reacting the prepolymer obtained in the step (1), 4' -xylene methane-5-maleimide and trihydric alcohol at 60 ℃ for 12 hours to obtain the thermoplastic polyurethane.
Preparation example 3
The thermoplastic polyurethane comprises the following components in parts by weight:
the preparation method of the thermoplastic polyurethane provided by the preparation example comprises the following steps:
(1) 1, 5-naphthalene diisocyanate, polytetrahydrofuran ether glycol, hydroxyl-terminated polydimethylsiloxane (CAS:70131-67-8), stannous isooctanoate, dibutyltin dilaurate and propylene diamine are reacted for 2 hours at 80 ℃ to obtain prepolymer;
(2) and (2) reacting the prepolymer obtained in the step (1), 4' -xylene methane-5-maleimide and trihydric alcohol at 40 ℃ for 6 hours to obtain the thermoplastic polyurethane.
Preparation example 4
A thermoplastic polyurethane which is different from preparation example 1 in that 1, 5-naphthalene diisocyanate is replaced with toluene diisocyanate and the other components, the amounts and the preparation method are the same as those of preparation example 1.
Preparation example 5
A thermoplastic polyurethane which is different from preparation example 1 in that polytetrahydrofuran ether glycol is added in an amount of 25 parts by weight, no hydroxy-terminated polydimethylsiloxane is added, and the other components, the amounts and the preparation method are the same as those of preparation example 1.
Preparation example 6
A thermoplastic polyurethane which is different from preparation example 1 in that 25 parts by weight of hydroxyl-terminated polydimethylsiloxane was added, polytetrahydrofuran ether glycol was not added, and the other components, the amounts and the preparation method were the same as those of preparation example 1.
Preparation example 7
A thermoplastic polyurethane which differs from example 1 in that propylene diamine is not added and the other components, amounts and preparation method are the same as those of preparation example 1.
Preparation example 8
A thermoplastic polyurethane which differs from example 1 in that no triol is added and the other components, amounts and preparation process are the same as in preparation example 1.
Example 1
A temperature-resistant thermoplastic polyurethane film comprises the following components in parts by weight:
the preparation method comprises the following steps: and (2) melting and extruding the thermoplastic polyurethane (preparation example 1), graphene, nano silicon dioxide, mica sheets, an anti-UV agent (UV-531), molybdenum disulfide, an antioxidant (antioxidant 1010) and erucamide at 180 ℃ through a single-screw extruder with the rotating speed of 50rpm, cooling and stretching to obtain the temperature-resistant thermoplastic polyurethane film.
Example 2
A temperature-resistant thermoplastic polyurethane film comprises the following components in parts by weight:
the preparation method comprises the following steps: and (2) melting and extruding the thermoplastic polyurethane (preparation example 2), graphene, nano silicon dioxide, mica sheets, an anti-UV agent (UV-531), molybdenum disulfide, an antioxidant (antioxidant 1010) and erucamide at 170 ℃ through a single-screw extruder with the rotating speed of 100rpm, cooling and stretching to obtain the temperature-resistant thermoplastic polyurethane film.
Example 3
A temperature-resistant thermoplastic polyurethane film comprises the following components in parts by weight:
the preparation method comprises the following steps: and (2) melting and extruding the thermoplastic polyurethane (preparation example 3), the graphene, the nano silicon dioxide, the mica sheet, the anti-UV agent (UV-531), the molybdenum disulfide, the antioxidant (antioxidant 1010) and the erucamide at 200 ℃ by a single-screw extruder with the rotating speed of 70rpm, cooling and stretching to obtain the temperature-resistant thermoplastic polyurethane film.
Example 4
A temperature-resistant thermoplastic polyurethane film which is different from example 1 only in that the thermoplastic polyurethane obtained in production example 4 is used in place of the thermoplastic polyurethane obtained in production example 1, and the other components, amounts and production methods are the same as in example 1.
Example 5
A temperature-resistant thermoplastic polyurethane film which differs from example 1 only in that the thermoplastic polyurethane obtained in production example 5 is used in place of the thermoplastic polyurethane obtained in production example 1, and the other components, amounts and production methods are the same as in example 1.
Example 6
A temperature-resistant thermoplastic polyurethane film which differs from example 1 only in that the thermoplastic polyurethane obtained in production example 6 is used in place of the thermoplastic polyurethane obtained in production example 1, and the other components, amounts and production methods are the same as in example 1.
Example 7
A temperature-resistant thermoplastic polyurethane film which differs from example 1 only in that the thermoplastic polyurethane obtained in production example 7 is used in place of the thermoplastic polyurethane obtained in production example 1, and the other components, amounts and production methods are the same as in example 1.
Example 8
A temperature-resistant thermoplastic polyurethane film which differs from example 1 only in that the thermoplastic polyurethane obtained in production example 8 is used in place of the thermoplastic polyurethane obtained in production example 1, and the other components, amounts and production methods are the same as in example 1.
Comparative example 1
A temperature-resistant thermoplastic polyurethane film, which is different from the thermoplastic polyurethane film in example 1 only in that graphene is not added, the addition amount of mica sheets is 15 parts by weight, and other components, the use amounts and the preparation method are the same as those in example 1.
Comparative example 2
A temperature-resistant thermoplastic polyurethane film, which is different from the thermoplastic polyurethane film in example 1 only in that the addition amount of graphene is 15 parts by weight, mica sheets are not added, and other components, the use amounts and the preparation method are the same as those in example 1.
Comparative example 3
A temperature-resistant thermoplastic polyurethane film, which is different from example 1 only in that the amount of graphene added is 15.5 parts by weight, nano-silica is not added, and other components, amounts and preparation methods are the same as those of example 1.
Comparative example 4
The temperature-resistant thermoplastic polyurethane film is different from the temperature-resistant thermoplastic polyurethane film in example 1 only in that the addition amount of nano silica is 23 parts by weight, graphene and mica sheets are not added, and other components, the use amounts and the preparation method are the same as those of example 1.
And (3) performance testing:
(1) elongation and tensile strength: testing according to the testing method provided by HG/T5070-2016;
(2) melting point: the test was performed by DSC.
The temperature-resistant thermoplastic polyurethane films provided in examples 1 to 8 and comparative examples 1 to 4 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the temperature-resistant thermoplastic polyurethane film provided by the invention has excellent mechanical properties and a higher melting point.
Specifically, the heat-resistant thermoplastic polyurethane films provided in examples 1 to 8 had a tensile strength of 34 to 40MPa, an elongation of 563 to 589%, and a melting point of 148 to 170 ℃.
Comparing example 1 with comparative examples 1 to 4, it can be found that the tensile strength, elongation and melting point of the temperature-resistant thermoplastic polyurethane film obtained in comparative examples 1 to 4 are much reduced compared with example 1, and it is proved that the temperature resistance and mechanical properties of the obtained polyurethane film are excellent only by adding the specific parts of graphene, mica sheets and nano silica defined by the invention in the preparation raw materials.
Further comparison of example 1 with example 4 shows that the polyurethane film obtained in example 1 has a higher melting point, indicating a better temperature resistance.
Further comparison of examples 1 and 5 to 6 revealed that the melting points of the polyurethane films obtained in examples 5 and 6 were lower than the melting point of the polyurethane film obtained in example 1.
Further comparison between example 1 and example 7 shows that the melting point of the polyurethane film obtained without propylene glycol is also lowered.
Further comparing example 1 with example 8, it can be seen that the melting point of the polyurethane film obtained without adding a triol as a chain extender is also lowered.
The applicant states that the present invention is illustrated by the above examples to a temperature-resistant thermoplastic polyurethane film and a method for preparing the same, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced by relying 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 temperature-resistant thermoplastic polyurethane film is characterized by comprising the following components in parts by weight:
2. the temperature-resistant thermoplastic polyurethane film according to claim 1, wherein the thermoplastic polyurethane is prepared from the following raw materials in parts by weight:
3. the temperature-resistant thermoplastic polyurethane film of claim 1 or 2, wherein the aromatic diisocyanate comprises 1, 5-naphthalene diisocyanate;
preferably, the catalyst comprises stannous isooctanoate and/or dibutyltin dilaurate;
preferably, the chain extender comprises any one of 4,4 ' -xylene methane-5-maleimide, 3 ' -dichloro-4, 4 ' -diphenylmethane diamine or hydroquinone bis-hydroxyethyl ether or a combination of at least two thereof; further preferred is 4,4 ' -xylylene-5-maleimide and/or 3,3 ' -dichloro-4, 4 ' -diphenylmethanediamine.
4. The temperature-resistant thermoplastic polyurethane film according to any one of claims 1 to 3, wherein the thermoplastic polyurethane is prepared from raw materials further comprising a cocatalyst and/or a crosslinking agent;
preferably, the content of the cocatalyst in the raw materials for preparing the thermoplastic polyurethane is 1-5 parts by weight;
preferably, the co-catalyst comprises propylene diamine;
preferably, the content of the cross-linking agent in the preparation raw material of the thermoplastic polyurethane is 1-5 parts by weight;
preferably, the cross-linking agent comprises a triol.
5. The temperature-resistant thermoplastic polyurethane film according to any one of claims 1 to 4, wherein the thermoplastic polyurethane is prepared by a method comprising the steps of:
(A1) reacting aromatic diisocyanate, polytetrahydrofuran ether glycol, hydroxyl-terminated polydimethylsiloxane, a catalyst and an optional cocatalyst to obtain a prepolymer;
(A2) and (2) reacting the prepolymer obtained in the step (1), a chain extender and an optional cross-linking agent to obtain the thermoplastic polyurethane.
6. The temperature-resistant thermoplastic polyurethane film according to claim 5, wherein the temperature of the reaction in the step (A1) is 70 to 80 ℃;
preferably, the reaction time of the step (A1) is 2-3 h;
preferably, the temperature of the reaction in the step (A2) is 40-60 ℃;
preferably, the reaction time of the step (A2) is 6-12 h.
7. The temperature-resistant thermoplastic polyurethane film according to any one of claims 1 to 6, wherein the material of the temperature-resistant thermoplastic polyurethane film further comprises any one or a combination of at least two of an abrasion-resistant additive, an antioxidant, a lubricant or a pigment;
preferably, the content of the wear-resistant additive in the material of the temperature-resistant thermoplastic polyurethane film is 1-5 parts by weight;
preferably, the anti-wear additive comprises any one or a combination of at least two of polytetrafluoroethylene fibers, molybdenum disulfide, graphite, or polyimide fibers;
preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
preferably, the content of the antioxidant in the material of the temperature-resistant thermoplastic polyurethane film is 1-5 parts by weight;
preferably, the content of the lubricant in the material of the temperature-resistant thermoplastic polyurethane film is 0.5-2 parts by weight;
preferably, the slip agent comprises any one or a combination of at least two of erucamide, oleamide, C wax, or montan wax;
preferably, the content of the pigment in the material of the temperature-resistant thermoplastic polyurethane film is 0.5-2 parts by weight;
preferably, the pigment includes any one of phthalocyanine red, phthalocyanine blue, phthalocyanine green, fast scarlet, macrored, macroyellow, permanent yellow, permanent violet, or azoic red or a combination of at least two thereof.
8. A method for preparing the temperature-resistant thermoplastic polyurethane film according to any one of claims 1 to 7, wherein the method comprises the following steps: and (2) melt-extruding, cooling and stretching thermoplastic polyurethane, graphene, nano silicon dioxide, mica sheets, an anti-UV agent, an optional wear-resistant additive, an optional antioxidant, an optional lubricant and an optional pigment to obtain the temperature-resistant thermoplastic polyurethane film.
9. The method according to claim 8, wherein the melt extrusion temperature is 170 to 200 ℃;
preferably, the pressure of the melt extrusion is 10-20 MPa;
preferably, the melt extrusion is performed by a single screw extruder;
preferably, the rotating speed of the single-screw extruder is 20-100 rpm.
10. The production method according to claim 8 or 9, characterized by comprising: the temperature-resistant thermoplastic polyurethane film is prepared by melt-extruding, cooling and stretching thermoplastic polyurethane, graphene, nano-silica, mica sheets, an anti-UV agent, an optional wear-resistant additive, an optional antioxidant, an optional lubricant and an optional pigment at 170-200 ℃ through a single-screw extruder with the rotating speed of 20-100 rpm.
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