CN109337350B - Temperature-resistant TPU film for automotive interior and preparation method thereof - Google Patents
Temperature-resistant TPU film for automotive interior and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Abstract
The invention provides a temperature-resistant TPU film for automotive interior and a preparation method thereof. The TPU film comprises the following raw material components in parts by mass: 50-70 parts of TPU particles, 20-30 parts of epoxy resin, 10-20 parts of melamine resin, 5-10 parts of porous ceramic particles and 3-8 parts of epoxy silane coupling agent. The TPU film is prepared by the steps of alcoholizing and acidifying porous ceramic particles, reacting with an epoxy silane coupling agent and melamine resin to form melamine resin coated porous ceramic particles, and then melting and blending the porous ceramic particles, the TPU particles and the epoxy resin. The TPU film provided by the invention has high mechanical strength and heat resistance, smooth surface and suitability for being used as an automobile interior material.
Description
Technical Field
The invention belongs to the technical field of TPU films, and particularly relates to a temperature-resistant TPU film for automotive interior and a preparation method thereof.
Background
Thermoplastic polyurethane elastomer (TPU) is a block material which has both plastic thermal plasticity and mechanical strength and rubber elasticity, and the application of the TPU in various industries is rapidly expanded due to excellent low temperature resistance, wear resistance and chemical corrosion resistance. Due to the advantages of diversity of raw material varieties, adjustability of molecular structures and the like, the thermoplastic polyurethane is widely applied to the industries of elastomers, foamed plastics, coatings, adhesives and the like. However, TPU has poor heat resistance, and the short-term use temperature of the TPU does not exceed 120 ℃, and the long-term use temperature of the TPU does not exceed 80 ℃, so that the use of the TPU in a certain temperature range is limited.
Some studies on improving the heat resistance of the TPU at home and abroad have been reported, and most of the studies design novel TPU materials from the perspective of changing the molecular chain structure of the TPU, but the method is complex, and the adopted raw materials are expensive, so that the cost of the TPU materials can be further increased. Another approach is to increase the heat resistance of the TPU by blending heat resistant materials. The method is simple, can be used for processing and modifying on the basis of the existing TPU material, has small influence on a factory production line, and is lower in cost. For example, CN 105315653a discloses a heat-resistant damping reinforced modified TPU composite material, which adopts a mixture of diatomite and montmorillonite as a heat-resistant composite filler to modify TPU; CN 106280392A discloses a high-temperature resistant TPU film, which is improved in heat resistance by adding white carbon black; CN107033797A discloses a high temperature resistant TPU film, which improves the heat resistance of TPU by adding aluminum phosphate powder and modified nano calcium carbonate. However, the compatibility between the inorganic particles and the TPU is poor, the mechanical strength of the TPU is greatly reduced while the heat resistance is improved, and the improvement effect on the heat resistance of the TPU is limited.
Therefore, if the mechanical strength of the TPU material can be improved while the heat resistance of the TPU material is improved, the application range of the TPU material will be further expanded.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a temperature-resistant TPU film for automotive interior and a preparation method thereof. The TPU film has high mechanical strength and heat resistance, smooth surface and is suitable for being used as an automotive interior material.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a temperature-resistant TPU film for automotive interior, which comprises the following raw material components in parts by mass:
according to the invention, porous ceramic particles, epoxy silane coupling agent and melamine resin are adopted to form melamine resin coated porous ceramic particles, the melamine resin coated porous ceramic particles have a micro-capsule structure, and the melamine resin on the surface and the porous ceramic particles jointly improve the heat resistance of the TPU film; on the other hand, the coating and bridging functions are realized, the compatibility of the porous ceramic particles and the matrix resin is improved, and the bonding of the porous ceramic particles and the matrix resin is realized. The invention takes the porous ceramic particles coated by the melamine resin as the additive, combines the epoxy resin, and modifies the TPU material, thereby improving the heat resistance and the mechanical strength of the TPU film and reducing the surface roughness.
In the present invention, the mass part of the TPU particles may be 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, or the like. .
The epoxy resin may be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, or the like by mass.
The melamine resin may be present in an amount of 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or the like by mass.
The porous ceramic particles may be present in an amount of 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, or the like by mass.
The epoxy silane coupling agent may be present in an amount of 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, or the like, by mass.
As a preferred technical scheme of the invention, the TPU film also comprises 1-3 parts (such as 1 part, 1.2 parts, 1.3 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.3 parts, 2.5 parts, 2.6 parts, 2.8 parts or 3 parts and the like) of antioxidant.
Preferably, the antioxidant is selected from one or a combination of at least two of tetrakis [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010), N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexamethylenediamine (antioxidant 1098), 2, 6-di-tert-butyl-p-cresol (antioxidant 264) or tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168); typical but non-limiting examples of such combinations are: a combination of antioxidant 1010 and antioxidant 1098, a combination of antioxidant 1010 and antioxidant 264, a combination of antioxidant 1010 and antioxidant 168, a combination of antioxidant 1098 and antioxidant 264, a combination of antioxidant 1098 and antioxidant 168, a combination of antioxidant 264 and antioxidant 168, and the like.
As a preferred embodiment of the present invention, the TPU particles are polyester TPU particles and/or polyether TPU particles.
In a preferred embodiment of the present invention, the epoxy resin is a bisphenol a epoxy resin.
Preferably, the epoxy value of the epoxy resin is 0.2 to 0.5; for example, it may be 0.2, 0.22, 0.23, 0.25, 0.26, 0.28, 0.3, 0.32, 0.33, 0.35, 0.36, 0.38, 0.4, 0.42, 0.43, 0.45, 0.46, 0.48, or 0.5, etc.
As a preferred embodiment of the present invention, the porous ceramic particles are selected from one or a combination of at least two of porous silica, porous alumina, or porous zirconia; typical but non-limiting examples of such combinations are: porous silica in combination with porous alumina, porous alumina in combination with porous zirconia, porous silica in combination with porous zirconia, and the like.
Preferably, the porous ceramic particles consist of porous alumina and porous zirconia according to the mass ratio of (3-6) to (4-7); for example, 3:7, 3.2:6.8, 3.5:6.5, 3.8:6.2, 4:6, 4.2:5.8, 4.5:5.5, 4.8:5.2, 5:5, 5.2:4.8, 5.5:4.5, 5.8:4.2, or 6:4, etc. may be mentioned.
When the porous alumina and the porous zirconia in the proportion are compounded to be used as porous ceramic particles, the heat resistance of the TPU film can be further improved.
Preferably, the particle size of the porous ceramic particles is 50 to 200 nm; for example, it may be 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 120nm, 130nm, 160nm, 180nm, or 200 nm.
In a preferred embodiment of the present invention, the epoxysilane coupling agent is gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and/or 3-glycidoxypropylmethyldiethoxysilane (KH-578).
In another aspect, the present invention provides a method for preparing the TPU film, comprising the steps of:
(1) carrying out alcoholization treatment and acidification treatment on the porous ceramic particles;
(2) adding the acidified porous ceramic particles obtained in the step (1) and an epoxy silane coupling agent into an alcohol solution, and reacting to obtain epoxy silane coupling agent modified porous ceramic particles;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting to form melamine resin coated porous ceramic particles;
(4) and (3) melting and blending the melamine resin coated porous ceramic particles, TPU particles, epoxy resin and optional antioxidant through an extruder, and then carrying out tape casting to obtain the TPU film.
As a preferred embodiment of the present invention, the alcoholization treatment in step (1) comprises: soaking in alcohol solution for 4-6 hr; for example, it may be 4h, 4.2h, 4.5h, 4.8h, 5h, 5.2h, 5.5h, 5.8h, or 6 h.
Preferably, the acidification treatment in step (1) is performed by: soaking in acid liquor for 3-5 h; for example, it may be 3h, 3.2h, 3.5h, 4h, 4.2h, 4.5h, 4.8h or 5 h.
Preferably, the acid solution is hydrochloric acid and/or sulfuric acid.
Preferably, the alcohol liquid used in step (1) and step (2) is independently selected from one or a combination of at least two of methanol, ethanol or butanol; typical but non-limiting examples of such combinations are methanol and ethanol, methanol and butanol, ethanol and butanol, and the like.
Preferably, the reaction temperature in step (2) is 20-40 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ or 40 ℃ and so on; the time is 15-30min, such as 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or 30 min.
As the preferred embodiment of the present invention, the reaction temperature in step (3) is 80-100 ℃, for example, 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 time is 30-60min, such as 30min, 32min, 33min, 35min, 36min, 38min, 40min, 42min, 43min, 45min, 46min, 48min, 50min, 52min, 53min, 55min, 56min, 58min or 60 min.
Preferably, the extruder in step (4) is a twin-screw extruder.
Preferably, the temperature of the melt blending in step (4) is 180-; for example, the temperature may be 180 ℃, 181 ℃, 182 ℃, 183 ℃, 184 ℃, 185 ℃, 186 ℃, 187 ℃, 188 ℃, 189 ℃, 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃, 195 ℃, 196 ℃, 197 ℃, 198 ℃, 199 ℃ or 200 ℃.
Preferably, the residence time of the material in the extruder is 5-8 min; for example, it may be 5min, 5.2min, 5.3min, 5.5min, 5.6min, 5.8min, 6min, 6.2min, 6.3min, 6.5min, 6.6min, 6.8min, 7min, 7.2min, 7.3min, 7.5min, 7.6min, 7.8min or 8 min.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) adding the porous ceramic particles into an alcohol solution, soaking for 4-6h, carrying out alcoholization treatment, then adding into an acid solution, soaking for 3-5h, and carrying out acidification treatment;
(2) adding the acidified porous ceramic particles obtained in the step (1) and an epoxy silane coupling agent into an alcohol solution, and reacting at 20-40 ℃ for 15-30min to obtain epoxy silane coupling agent modified porous ceramic particles;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting at 80-100 ℃ for 30-60min to form melamine resin coated porous ceramic particles;
(4) adding the porous ceramic particles coated by the melamine resin, TPU particles, epoxy resin and optional antioxidant into a double-screw extruder, controlling the material residence time to be 5-8min, melting and blending at the temperature of 180-200 ℃, and then carrying out tape casting to obtain the TPU film.
In the process of melt blending in the step (4), the melamine resin can react with the epoxy resin and the TPU to realize the bonding of the porous ceramic particles and the matrix material, and the partial crosslinking of the matrix material is realized to improve the mechanical strength.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the porous ceramic particles coated with the melamine resin and having a micro-capsule structure are formed by adopting the porous ceramic particles, the epoxy silane coupling agent and the melamine resin, and then the TPU material is modified by combining the epoxy resin, so that the heat resistance and the mechanical strength of the TPU film are improved. The TPU film provided by the invention has a smooth surface, the tensile strength of the TPU film is 42-50MPa, the elongation at break is 350-400%, the thermal weight loss at 250 ℃ is 2-6%, and the thermal weight loss at 300 ℃ is 30-53%; by optimizing the components of the porous ceramic particles, the heat resistance of the TPU film can be further improved, the thermal weight loss at 250 ℃ is 2-3%, the thermal weight loss at 300 ℃ is 30-35%, and the TPU film is suitable for being used as an automotive interior material.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. 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 embodiment provides a temperature-resistant TPU film for automotive interiors, which comprises the following raw material components in parts by mass:
wherein the epoxy value of the bisphenol A type epoxy resin is 0.2, and the particle sizes of the porous alumina and the porous zirconia are both 50-100 nm.
The preparation method of the TPU film comprises the following steps:
(1) adding porous alumina and porous zirconia into ethanol, soaking for 4h, carrying out alcoholization treatment, then adding into sulfuric acid, soaking for 5h, and carrying out acidification treatment;
(2) adding the acidified porous ceramic particles obtained in the step (1) and KH-560 into ethanol, and reacting at 20 ℃ for 30min to obtain porous ceramic particles modified by epoxy silane coupling agent;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting at 80 ℃ for 60min to form melamine resin coated porous ceramic particles;
(4) adding the melamine resin coated porous ceramic particles, polyester type TPU particles and bisphenol A type epoxy resin into a double-screw extruder, controlling the material residence time to be 5min, melting and blending at 200 ℃, and then carrying out tape casting to obtain the temperature-resistant TPU film for automobile interior decoration.
Example 2
The embodiment provides a temperature-resistant TPU film for automotive interiors, which comprises the following raw material components in parts by mass:
wherein the epoxy value of the bisphenol A type epoxy resin is 0.3, and the particle sizes of the porous alumina and the porous zirconia are both 50-100 nm.
The preparation method of the TPU film comprises the following steps:
(1) adding porous alumina and porous zirconia into ethanol, soaking for 6h, carrying out alcoholization treatment, then adding into sulfuric acid, soaking for 3h, and carrying out acidification treatment;
(2) adding the acidified porous ceramic particles obtained in the step (1) and KH-560 into ethanol, and reacting at 40 ℃ for 15min to obtain porous ceramic particles modified by epoxy silane coupling agent;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting for 30min at 100 ℃ to form melamine resin coated porous ceramic particles;
(4) adding the melamine resin coated porous ceramic particles, polyester type TPU particles, bisphenol A type epoxy resin and an antioxidant into a double-screw extruder, controlling the material residence time to be 8min, melting and blending at 180 ℃, and then carrying out tape casting to obtain the temperature-resistant TPU film for the automotive interior.
Example 3
The embodiment provides a temperature-resistant TPU film for automotive interiors, which comprises the following raw material components in parts by mass:
wherein the epoxy value of the bisphenol A type epoxy resin is 0.5, and the particle sizes of the porous alumina and the porous zirconia are both 50-100 nm.
The preparation method of the TPU film comprises the following steps:
(1) adding porous alumina and porous zirconia into ethanol, soaking for 5h, carrying out alcoholization treatment, then adding into sulfuric acid, soaking for 4h, and carrying out acidification treatment;
(2) adding the acidified porous ceramic particles obtained in the step (1) and KH-560 into ethanol, and reacting at 30 ℃ for 20min to obtain porous ceramic particles modified by epoxy silane coupling agent;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting at 90 ℃ for 40min to form melamine resin coated porous ceramic particles;
(4) and adding the melamine resin coated porous ceramic particles, polyester type TPU particles, bisphenol A type epoxy resin and an antioxidant into a double-screw extruder, controlling the retention time of the materials to be 6min, melting and blending at 190 ℃, and then carrying out tape casting to obtain the temperature-resistant TPU film for the automotive interior.
Example 4
The embodiment provides a temperature-resistant TPU film for automotive interiors, which comprises the following raw material components in parts by mass:
wherein the epoxy value of the bisphenol A type epoxy resin is 0.2, and the particle sizes of the porous alumina and the porous zirconia are both 100-200 nm.
The preparation method of the TPU film comprises the following steps:
(1) adding porous alumina and porous zirconia into ethanol, soaking for 4.5h, carrying out alcoholization treatment, then adding into sulfuric acid, soaking for 4.5h, and carrying out acidification treatment;
(2) adding the acidified porous ceramic particles obtained in the step (1) and KH-578 into ethanol, and reacting at 25 ℃ for 25min to obtain porous ceramic particles modified by epoxy silane coupling agent;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting at 85 ℃ for 45min to form melamine resin coated porous ceramic particles;
(4) adding the melamine resin coated porous ceramic particles, polyether TPU particles, bisphenol A epoxy resin and an antioxidant into a double-screw extruder, controlling the material residence time to be 7min, melting and blending at 185 ℃, and then carrying out tape casting to obtain the temperature-resistant TPU film for the automotive interior.
Example 5
The embodiment provides a temperature-resistant TPU film for automotive interiors, which comprises the following raw material components in parts by mass:
wherein the epoxy value of the bisphenol A type epoxy resin is 0.3, and the particle sizes of the porous alumina and the porous zirconia are both 100-200 nm.
The preparation method of the TPU film comprises the following steps:
(1) adding porous alumina and porous zirconia into ethanol, soaking for 5h, carrying out alcoholization treatment, then adding into sulfuric acid, soaking for 5h, and carrying out acidification treatment;
(2) adding the acidified porous ceramic particles obtained in the step (1) and KH-578 into ethanol, and reacting at 35 ℃ for 15min to obtain porous ceramic particles modified by epoxy silane coupling agent;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting at 95 ℃ for 35min to form melamine resin coated porous ceramic particles;
(4) adding the melamine resin coated porous ceramic particles, polyether TPU particles, bisphenol A epoxy resin and an antioxidant into a double-screw extruder, controlling the material residence time to be 5min, melting and blending at 180 ℃, and then carrying out tape casting to obtain the temperature-resistant TPU film for the automotive interior.
Example 6
The embodiment provides a temperature-resistant TPU film for automotive interiors, which comprises the following raw material components in parts by mass:
wherein the epoxy value of the bisphenol A type epoxy resin is 0.5, and the particle sizes of the porous alumina and the porous zirconia are both 100-200 nm.
The preparation method of the TPU film comprises the following steps:
(1) adding porous alumina and porous zirconia into ethanol, soaking for 6h, carrying out alcoholization treatment, then adding into sulfuric acid, soaking for 3h, and carrying out acidification treatment;
(2) adding the acidified porous ceramic particles obtained in the step (1) and KH-578 into ethanol, and reacting at 25 ℃ for 30min to obtain porous ceramic particles modified by epoxy silane coupling agent;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting for 45min at 100 ℃ to form melamine resin coated porous ceramic particles;
(4) adding the melamine resin coated porous ceramic particles, polyether TPU particles, bisphenol A epoxy resin and an antioxidant into a double-screw extruder, controlling the material residence time to be 8min, melting and blending at 180 ℃, and then carrying out tape casting to obtain the temperature-resistant TPU film for automotive interior.
Example 7
The difference from example 1 is that the porous ceramic particles are only 10 parts porous alumina; other raw materials, amounts and preparation methods were the same as those of example 1.
Example 8
The difference from example 1 is that the porous ceramic particles are only 10 parts of porous zirconia; other raw materials, amounts and preparation methods were the same as those of example 1.
Example 9
The difference from example 1 is that the porous ceramic particles are only 10 parts of porous silica; other raw materials, amounts and preparation methods were the same as those of example 1.
Comparative example 1
The difference from example 1 is that melamine resin is not contained; other raw materials, amounts and preparation methods were the same as those of example 1.
Comparative example 2
Differs from example 1 in that KH-560 is not contained; other raw materials, amounts and preparation methods were the same as those of example 1.
Comparative example 3
The difference from example 1 is that the total amount of porous alumina and porous zirconia was 13 parts; other raw materials, amounts and preparation methods were the same as those of example 1.
Comparative example 4
The difference from the example 1 is that the mass part of the bisphenol A type epoxy resin is 35 parts; other raw materials, amounts and preparation methods were the same as those of example 1.
The TPU films provided in the above examples and comparative examples were tested for heat resistance and mechanical properties according to the following test methods/standards:
thermal weight loss: respectively measuring the thermal weight loss of the TPU film at 250 ℃ and 300 ℃ at a heating rate of 10 ℃/min by adopting a differential scanning calorimeter;
tensile strength and elongation at break: GB/T528-2009.
The results of the above tests are shown in table 1 below:
TABLE 1
| Test items | 250 ℃ loss on heating (%) | 300 ℃ loss on heating (%) | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 1 | 2.3 | 32.5 | 48 | 360 |
| Example 2 | 2.8 | 34.3 | 46 | 373 |
| Example 3 | 2.7 | 33.6 | 47 | 355 |
| Example 4 | 2.2 | 31.7 | 42 | 389 |
| Example 5 | 2.5 | 34.5 | 42 | 394 |
| Example 6 | 2.6 | 33.2 | 43 | 396 |
| Example 7 | 5.7 | 50.8 | 47 | 375 |
| Example 8 | 5.5 | 48.6 | 48 | 368 |
| Example 9 | 6 | 52.4 | 46 | 352 |
| Comparative example 1 | 9.5 | 63.7 | 21 | 228 |
| Comparative example 2 | 8.3 | 59.4 | 28 | 286 |
| Comparative example 3 | 2.2 | 32.3 | 44 | 342 |
| Comparative example 4 | 6.4 | 58.3 | 48 | 352 |
As can be seen from the results in Table 1, the TPU film with high heat resistance and mechanical strength is obtained by matching the raw materials in a specific ratio; by optimizing the components of the porous ceramic particles, the heat resistance of the TPU film can be further improved. When the melamine resin or the epoxy silane coupling agent was not added (comparative examples 1 and 2), the structure of the melamine resin-coated porous ceramic particles could not be formed, resulting in a significant decrease in both the heat resistance and the mechanical strength of the TPU film. When the content of the porous ceramic particles was excessive (comparative example 3), the heat resistance of the TPU film was not significantly improved, but the mechanical properties were significantly deteriorated. When the content of the epoxy resin was too large (comparative example 4), the heat resistance of the TPU film was remarkably decreased.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (15)
1. The temperature-resistant TPU film for the automotive interior is characterized by comprising the following raw material components in parts by mass:
the porous ceramic particles consist of porous alumina and porous zirconia according to the mass ratio of (3-6) to (4-7), and the particle size of the porous ceramic particles is 50-200 nm;
carrying out alcoholization treatment and acidification treatment on the porous ceramic particles; the alcoholization treatment method comprises the following steps: soaking in alcohol solution selected from one or combination of at least two of methanol, ethanol or butanol for 4-6 h; the acidification treatment method comprises the following steps: soaking in acid solution (hydrochloric acid and/or sulfuric acid) for 3-5 hr.
2. The TPU film of claim 1 further comprising 1 to 3 parts of an antioxidant.
3. The TPU film of claim 2 wherein the antioxidant is selected from the group consisting of tetrakis [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine, 2, 6-di-tert-butyl-p-cresol or tris (2, 4-di-tert-butylphenyl) phosphite, or a combination of at least two thereof.
4. The TPU film of claim 1 wherein the TPU particles are polyester TPU particles and/or polyether TPU particles.
5. The TPU film of claim 1 wherein the epoxy resin is a bisphenol a type epoxy resin.
6. The TPU film of claim 1 wherein the epoxy resin has an epoxy value of 0.2 to 0.5.
7. The TPU film of claim 1, wherein the epoxysilane coupling agent is gamma- (2, 3-glycidoxy) propyltrimethoxysilane and/or 3-glycidoxypropylmethyldiethoxysilane.
8. The process for preparing the TPU film of any of claims 1-7, comprising the steps of:
(1) carrying out alcoholization treatment and acidification treatment on the porous ceramic particles; the alcoholization treatment method comprises the following steps: soaking in alcohol solution selected from one or combination of at least two of methanol, ethanol or butanol for 4-6 h; the acidification treatment method comprises the following steps: soaking in acid liquor for 3-5h, wherein the acid liquor is hydrochloric acid and/or sulfuric acid;
(2) adding the acidified porous ceramic particles obtained in the step (1) and an epoxy silane coupling agent into an alcohol solution, and reacting to obtain epoxy silane coupling agent modified porous ceramic particles;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting to form melamine resin coated porous ceramic particles;
(4) and (3) melting and blending the melamine resin coated porous ceramic particles, TPU particles, epoxy resin and optional antioxidant through an extruder, and then carrying out tape casting to obtain the TPU film.
9. The method according to claim 8, wherein the alcohol solution used in step (2) is selected from one or a combination of at least two of methanol, ethanol, and butanol.
10. The method according to claim 8, wherein the reaction in the step (2) is carried out at a temperature of 20 to 40 ℃ for 15 to 30 min.
11. The method according to claim 8, wherein the reaction in the step (3) is carried out at a temperature of 80 to 100 ℃ for 30 to 60 minutes.
12. The production method according to claim 8, wherein the extruder in the step (4) is a twin-screw extruder.
13. The production method as claimed in claim 8, wherein the temperature of the melt blending in the step (4) is 180-200 ℃.
14. The method of claim 8, wherein the residence time of the material in the extruder is 5-8 min.
15. The method of any one of claims 8 to 14, comprising the steps of:
(1) adding the porous ceramic particles into an alcohol solution, soaking for 4-6h, and carrying out alcoholization treatment, wherein the alcohol solution is one or a combination of at least two of methanol, ethanol or butanol; then adding the mixture into acid liquor for soaking for 3-5h, and carrying out acidification treatment, wherein the acid liquor is hydrochloric acid and/or sulfuric acid;
(2) adding the acidified porous ceramic particles obtained in the step (1) and an epoxy silane coupling agent into an alcohol solution, and reacting at 20-40 ℃ for 15-30min to obtain epoxy silane coupling agent modified porous ceramic particles;
(3) mixing the porous ceramic particles modified by the epoxy silane coupling agent with melamine resin, and reacting at 80-100 ℃ for 30-60min to form melamine resin coated porous ceramic particles;
(4) adding the porous ceramic particles coated by the melamine resin, TPU particles, epoxy resin and optional antioxidant into a double-screw extruder, controlling the material residence time to be 5-8min, melting and blending at the temperature of 180-200 ℃, and then carrying out tape casting to obtain the TPU film.
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| CN112226066B (en) * | 2020-09-22 | 2021-09-24 | 东莞市雄林新材料科技股份有限公司 | TPU (thermoplastic polyurethane) anti-slip gasket and preparation method thereof |
| WO2023017738A1 (en) * | 2021-08-13 | 2023-02-16 | ビーエスティー スペシャリティー カンパニー リミテッド | Latex composition for dip molding, and method for producing dip-molded article |
| CN114437533A (en) * | 2022-01-26 | 2022-05-06 | 昆山红苹果塑胶新材料有限公司 | High-resilience TPU film and production process thereof |
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