CN113307994A - High-elasticity and high-moisture-permeability TPU film and preparation method thereof - Google Patents
High-elasticity and high-moisture-permeability TPU film and preparation method thereof Download PDFInfo
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- CN113307994A CN113307994A CN202110482734.8A CN202110482734A CN113307994A CN 113307994 A CN113307994 A CN 113307994A CN 202110482734 A CN202110482734 A CN 202110482734A CN 113307994 A CN113307994 A CN 113307994A
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention provides a high-elasticity and high-moisture-permeability TPU film and a preparation method thereof, wherein the preparation raw materials of the TPU film comprise a combination of perfluoropolyether diol, aliphatic diisocyanate, a chain extender, a catalyst, polystyrene, a foaming silicone master batch, an abrasion-resistant additive and an anti-UV agent; the TPU is generated by adopting perfluoropolyether diol, aliphatic diisocyanate and a chain extender in specific parts under the condition of a catalyst, and the polystyrene in specific parts added in the preparation raw materials is matched, so that the moisture permeability of the finally obtained TPU film is enhanced; and the foaming silicone master batch is added in the preparation raw materials, so that the elasticity of the TPU film is enhanced, the TPU film with excellent elasticity and moisture permeability is finally obtained, and the method has important research significance.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a high-elasticity and high-moisture-permeability TPU film and a preparation method thereof.
Background
The TPU material is increasingly popular with people due to the excellent performance and environmental protection performance, not only has the excellent characteristics of high tension, high tensile force, toughness and aging resistance, but also is a mature environmental protection material, and at present, the TPU material is widely applied to: shoe materials, ready-made clothes, inflatable toys, aquatic and underwater sports equipment, medical equipment, fitness equipment, automobile seat materials, umbrellas, leather suitcases, leather bags and the like.
The halogen-free flame-retardant TPU can also replace soft PVC to meet the environmental protection requirements of more and more fields. The TPU elastomer is a special type of elastomer, has wide hardness range and wide performance range, is a high molecular material between rubber and plastic, can be plasticized by heating, has no or little crosslinking on a chemical structure, and has basically linear molecules but certain physical crosslinking. Therefore, the elasticity of TPU materials is not particularly desirable. CN109401281A discloses a high-elasticity TPU film and a preparation method thereof, wherein the preparation method of the high-elasticity TPU film comprises the steps of mixing prepared TPU particles, foaming silicone master batches and modified nano silicon dioxide master batches in three stages according to a ratio, then conveying the mixture into a casting machine through an automatic feeding system, and extruding the mixture to form the film. The TPU film provided by the invention has high elasticity, and can be widely applied to the fields of damping materials, packaging toys, children toys, sports goods, aeromodels, heat-insulating materials, automobile interior materials and the like. However, the product produced by the TPU material obtained in the patent has low moisture permeability, and cannot quickly discharge sweat emitted by a human body in hot weather so as to provide dry and comfortable comfort for the skin.
CN107043531A discloses a TPU film with good moisture permeability, which comprises the following materials: perfluoropolyether diol, a chain extender, aliphatic diisocyanate, TPO resin, color master batch, an antioxidant, a light stabilizer, an anti-yellowing agent, erucamide, oleamide and stearic acid. The preparation method of the TPU film comprises the following steps: 1) preparing a fluorine-containing TPU; 2) uniformly stirring the fluorine-containing TPU, TPO resin, color master batch, antioxidant, anti-yellowing agent, erucamide, oleamide and stearic acid; 3) and (3) adding the material obtained in the step (2) into an internal mixer for internal mixing for 5-10 minutes, and extruding through an extruder. CN112497877A discloses a waterproof moisture-permeable compound TPU film, which comprises the following raw materials in parts by weight: the material comprises the following raw materials in parts by weight: thermoplastic polyurethane: 100-120 parts; 50-70 parts of polystyrene; 40-60 parts of polyisobutylene; 50-60 parts of dimethyl terephthalate; 50-60 parts of ethylene glycol; 10-20 parts of a catalyst; 30-40 parts of polypropylene; 50-60 parts of triethanolamine; 3-5 parts of azodiisobutyronitrile; 10-20 parts of methanol; 25-35 parts of polytetrafluoroethylene; 5-9 parts of a curing agent; and the balance of water, and putting the raw materials into a reaction kettle for reaction according to the steps. The invention can realize the composite TPU film integrating the moisture permeability and the waterproof performance, and the material layer A in the composite TPU film can ensure that the composite TPU film has higher strength, durability and chemical corrosion resistance, but the moisture permeability of the TPU films prepared by the two patents still needs to be improved, and the elasticity is poor.
Therefore, the development of a TPU film having both excellent elasticity and moisture permeability is an urgent technical problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-elasticity and high-moisture-permeability TPU film and a preparation method thereof, wherein the preparation raw materials of the high-elasticity and high-moisture-permeability TPU film comprise perfluoropolyether diol and aliphatic diisocyanate in specific parts, and polystyrene in specific parts is added in a matched manner, so that the moisture permeability of the prepared TPU film is enhanced; the foaming silicone master batch with characteristic parts is added into the raw materials, so that the elasticity of the TPU film is enhanced, and the TPU film with excellent elasticity and moisture permeability is finally obtained, and the method has important research significance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-elasticity and high-moisture-permeability TPU film, which comprises the following raw materials in parts by weight:
the perfluoropolyether diol can be 33 parts by weight, 36 parts by weight, 39 parts by weight, 43 parts by weight, 46 parts by weight, 49 parts by weight, 53 parts by weight, 56 parts by weight, or 59 parts by weight, and specific values therebetween, not to be limiting in space and for brevity, the invention is not exhaustive of the specific values included in the ranges.
The aliphatic diisocyanate may be 53 parts by weight, 56 parts by weight, 59 parts by weight, 63 parts by weight, 66 parts by weight, 69 parts by weight, 73 parts by weight, 76 parts by weight, or 79 parts by weight, and specific points therebetween are not exhaustive for the purpose of brevity and disclosure, and the specific points included in the ranges are not exhaustive.
The chain extender may be 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14 or 14.5 parts by weight, and the specific points therebetween, limited to space and for brevity, are not exhaustive of the specific points included in the ranges set forth.
The catalyst may be present in an amount of 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, and specific values therebetween, not to limit the invention to the space and for brevity, the specific values included in the ranges are not exhaustive.
The polystyrene may be 17 parts by weight, 19 parts by weight, 21 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, or 29 parts by weight, and specific values therebetween are not exhaustive for the invention and are included for brevity.
The foaming silicone master batch can be 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight or 2.8 parts by weight, and specific values therebetween, and the invention is not exhaustive and for the sake of brevity only, specific values included in the ranges are not intended to be exhaustive.
The anti-wear additive may be 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, or 9.5 parts by weight, and specific points therebetween, not to mention the space and for brevity, the invention is not exhaustive of the specific points included in the ranges.
The UV resistant agent may be 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 parts by weight, and specific points therebetween, not to be construed as being exhaustive of the specific points included in the range for brevity and clarity.
On one hand, the high-elasticity and high-moisture-permeability TPU film provided by the invention is used for preparing the TPU material by selecting perfluoropolyether diol and aliphatic diisocyanate in the preparation raw materials under the condition of a catalyst, and polar groups are introduced into TPU molecules, so that the hydrophilicity of the prepared TPU material is improved; furthermore, polystyrene with a specific part is added into the preparation raw materials of the TPU film, the coordination and matching between the inside and outside molecules, the molecular structure design and the selection of an auxiliary agent are adopted, and the hydrophilicity of the TPU film is further improved, so that the TPU film can adsorb water molecules in a high-humidity environment and can be transferred to a low-humidity environment for desorption through chain segment motion.
On the other hand, the TPU material is a high molecular material between rubber and plastic, can be heated and plasticized, has no or little crosslinking on a chemical structure, and has basically linear molecules, so the elasticity is poor.
The high elasticity in the high-elasticity and high-moisture-permeability TPU film provided by the invention refers to the TPU film with 100% definite elongation recovery rate not less than 90%; "high moisture permeability" refers to the mass of water vapor passing through a sample per unit area under a prescribed temperature condition, that is, the moisture permeability is not less than 9050g/m224h TPU film.
Preferably, the aliphatic diisocyanate includes any one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, or methylcyclohexane diisocyanate, or a combination of at least two thereof.
Preferably, the chain extender comprises 1,4 butanediol.
Preferably, the catalyst comprises an organotin catalyst, and one or a combination of at least two of CT-E229, stannous octoate and dibutyltin dilaurate may be selected.
Preferably, the polystyrene has a particle size of 200 to 300 meshes, such as 210 meshes, 220 meshes, 230 meshes, 240 meshes, 250 meshes, 260 meshes, 270 meshes, 280 meshes or 290 meshes, and specific values therebetween are limited to space and for brevity, and the specific values included in the range are not exhaustive.
As a preferred technical scheme, the TPU film prepared when the particle size of the polystyrene provided by the invention is 200-300 meshes has excellent elasticity and moisture absorption performance; on one hand, if the particle size of the polystyrene is less than 200 meshes, the polystyrene is easy to agglomerate, and the elasticity and the hygroscopicity of the TPU film are influenced; on the other hand, if the particle size of the polystyrene is larger than 300 mesh, the moisture absorption of the TPU film is affected.
Preferably, the preparation raw materials of the foaming silicone master batch comprise the following components in parts by weight:
90-100 parts by weight of TPU particles;
2-10 parts by weight of a foaming agent;
80-90 parts of silicone powder.
The TPU particles can be 91, 92, 93, 94, 95, 96, 97, 98, or 99 parts by weight, and the specific points therebetween are not exhaustive of the ranges included for brevity and clarity.
Preferably, the mass ratio of the TPU particles to the silicone powder is 1 (0.8-1.2), such as 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1 or 1: 1.15.
Preferably, the blowing agent comprises any one of carbon dioxide, nitrogen, propane, n-butane, isobutane, n-pentane or isopentane, or a combination of at least two thereof.
Preferably, the foaming silicone master batch is prepared by the following method, and the method comprises the following steps: and mixing the TPU particles, the foaming agent and the silicone powder, and extruding to obtain the foaming silicone master batch.
Preferably, the anti-wear additive comprises any one or a combination of at least two of polytetrafluoroethylene fibers, molybdenum disulfide, graphite, or polyimide fibers, and further preferably polytetrafluoroethylene fibers and/or polyimide fibers.
Preferably, the anti-UV agent includes any one of a salicylate-based anti-UV agent, a benzophenone-based anti-UV agent, a benzotriazole-based anti-UV agent, a substituted acrylonitrile-based anti-UV agent, a triazine-based anti-UV agent, or a hindered amine-based anti-UV agent, or a combination of at least two thereof.
Preferably, the raw materials for preparing the high-elasticity and high-moisture-permeability TPU film also comprise any one or a combination of at least two of an antioxidant, a lubricant or a pigment.
Preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Preferably, the antioxidant is contained in the raw material for preparing the high-elasticity and high-moisture-permeability TPU 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 and conciseness.
Preferably, the amount of the lubricant in the raw material for preparing the high-elasticity and high-moisture-permeability TPU 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 the invention is not limited to the specific values included in the ranges for brevity and conciseness.
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 content of the raw material for preparing the high-elasticity and high-moisture-permeability TPU 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 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 high elasticity and high moisture permeability TPU film of the first aspect, which comprises the following steps:
(1) reacting perfluoropolyether diol, aliphatic diisocyanate and a catalyst to obtain a prepolymer;
(2) reacting the prepolymer obtained in the step (1) with a chain extender, and extruding to obtain TPU resin;
(3) and (3) melting, extruding, cooling and stretching the TPU resin obtained in the step (2), polystyrene, foaming silicone master batch, an abrasion-resistant additive, an anti-UV agent, an optional antioxidant, an optional lubricant and an optional pigment to obtain the high-elasticity and high-moisture-permeability TPU film.
Preferably, the reaction temperature in step (1) 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 in step (1) 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, the invention does not provide an exhaustive list of the specific values included in the range.
Preferably, the reaction temperature in step (2) is 40-60 ℃, 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 in step (2) 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, the invention is not intended to be limited to the specific values included in the range.
Preferably, the melt extrusion temperature in step (3) 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 range.
Preferably, the melt extrusion pressure in step (3) is 10-20 Mpa, such as 11Mpa, 12Mpa, 13Mpa, 14Mpa, 15Mpa, 16Mpa, 17Mpa, 18Mpa or 19Mpa, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive.
Preferably, the melt extrusion of step (3) 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:
(1) reacting perfluoropolyether diol, aliphatic diisocyanate and a catalyst at 70-80 ℃ for 2-3 hours to obtain a prepolymer;
(2) reacting the prepolymer obtained in the step (1) with a chain extender at the temperature of 40-60 ℃ for 6-12 h, and extruding to obtain TPU resin;
(3) and (3) melting and extruding the TPU resin obtained in the step (2), polystyrene, foaming silicone master batches, an abrasion-resistant additive, an anti-UV agent, 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, cooling and stretching to obtain the high-elasticity and high-TPU moisture-permeable film.
Compared with the prior art, the invention has the following beneficial effects:
the TPU film with high elasticity and high moisture permeability provided by the invention adopts perfluoropolyether diol, aliphatic diisocyanate and a chain extender in specific parts to generate a TPU material under the condition of a catalyst, and introduces polar groups into a TPU molecular chain to improve the hydrophilicity of the TPU film; the moisture permeability of the TPU film is further enhanced by matching the polystyrene with a specific part added in the raw materials for preparation; furthermore, foaming silicone master batches with characteristic parts are added into the raw materials, so that the elasticity of the TPU film is enhanced, and the TPU film with excellent elasticity and moisture permeability is finally obtained; specifically, the moisture permeability of the TPU film provided by the invention is 9050-10500 g/m2 & 24 h; the 100% definite elongation recovery rate is 90-98%; the elongation at break is 468-490%, completely meets the market requirements, and has important research significance.
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
A foaming silicone master batch comprises the following components in parts by weight:
95 parts by weight of TPU particles;
5 parts by weight of a foaming agent;
85 parts of silicone powder;
the preparation method comprises the following steps: mixing TPU particles (S90A), a foaming agent (ethanol) and silicone powder, and extruding at 180 ℃ to obtain the foaming silicone master batch.
Preparation example 2
A foaming silicone master batch comprises the following components in parts by weight:
90 parts by weight of TPU particles;
2 parts by weight of a foaming agent;
80 parts of silicone powder;
the preparation method comprises the following steps: mixing TPU particles (S90A), a foaming agent (ethanol) and silicone powder, and extruding at 180 ℃ to obtain the foaming silicone master batch.
Preparation example 3
A foaming silicone master batch comprises the following components in parts by weight:
100 parts by weight of TPU particles;
2 parts by weight of a foaming agent;
90 parts by weight of silicone powder;
the preparation method comprises the following steps: mixing TPU particles (S90A), a foaming agent (ethanol) and silicone powder, and extruding at 180 ℃ to obtain the foaming silicone master batch.
Preparation example 4
A foamed silicone master batch which differs from preparation example 1 only in that the addition amount of TPU particles is 110 parts by weight, the addition amount of silicone powder is 70 parts by weight, and the other components, the amounts and the preparation method are the same as those of preparation example 1.
Preparation example 5
A foamed silicone master batch which differs from preparation example 1 only in that the addition amount of TPU particles is 80 parts by weight, the addition amount of silicone powder is 100 parts by weight, and the other components, the amounts and the preparation method are the same as those of preparation example 1.
Comparative preparation example 1
A silicone master batch which is different from preparation example 1 in that a foaming agent is not added, and other components, the amount and the preparation method are the same as those of preparation example 1.
Example 1
A high-elasticity and high-moisture-permeability TPU film comprises the following preparation raw materials in parts by weight:
the preparation method of the high-elasticity and high-moisture-permeability TPU film provided by the embodiment comprises the following steps:
(1) reacting perfluoropolyether diol (Dow chemical), isophorone diisocyanate and a catalyst (CT-E229) at 75 ℃ for 2.5 hours to obtain a prepolymer;
(2) reacting the prepolymer obtained in the step (1) with 1, 4-butanediol at 50 ℃ for 10.5h, and extruding to obtain TPU resin;
(3) and (3) melting and extruding the TPU resin obtained in the step (2), polystyrene (HIPS 622P of Shanghai Sicacao), foaming silicone master batches (preparation example 1), molybdenum disulfide, an anti-UV agent (UV-531), an antioxidant (antioxidant 1010), erucamide and a pigment (phthalocyanine blue) at 180 ℃ through a single-screw extruder with the rotating speed of 80rpm, cooling and stretching to obtain the high-elasticity and high-moisture-permeability TPU film.
Example 2
A high-elasticity and high-moisture-permeability TPU film comprises the following preparation raw materials in parts by weight:
the preparation method of the high-elasticity and high-moisture-permeability TPU film provided by the embodiment comprises the following steps:
(1) reacting perfluoropolyether diol (Dow chemical), isophorone diisocyanate and a catalyst (CT-E229) at 70 ℃ for 3 hours to obtain a prepolymer;
(2) reacting the prepolymer obtained in the step (1) with 1, 4-butanediol at 40 ℃ for 12h, and extruding to obtain TPU resin;
(3) and (3) melting and extruding the TPU resin obtained in the step (2), polystyrene (HIPS 622P of Shanghai Sicacao, 250 meshes), foaming silicone master batch (preparation example 2), molybdenum disulfide, an anti-UV agent (UV-531), an antioxidant (antioxidant 1010), erucamide and a pigment (phthalocyanine blue) at 170 ℃ by a single-screw extruder with the rotating speed of 100rpm, cooling and stretching to obtain the high-elasticity and high-moisture-permeability TPU film.
Example 3
A high-elasticity and high-moisture-permeability TPU film comprises the following preparation raw materials in parts by weight:
the preparation method of the high-elasticity and high-moisture-permeability TPU film provided by the embodiment comprises the following steps:
(1) reacting perfluoropolyether diol (Dow chemical), isophorone diisocyanate and a catalyst (CT-E229) at 80 ℃ for 2h to obtain a prepolymer;
(2) reacting the prepolymer obtained in the step (1) with 1, 4-butanediol at 60 ℃ for 6 hours, and extruding to obtain TPU resin;
(3) and (3) melting and extruding the TPU resin obtained in the step (2), polystyrene (HIPS 622P of Shanghai Sicaike, 300 meshes), foaming silicone master batch (preparation example 3), molybdenum disulfide, an anti-UV agent (UV-531), an antioxidant (antioxidant 1010), erucamide and a pigment (phthalocyanine blue) at 200 ℃ by a single-screw extruder with the rotating speed of 20rpm, cooling and stretching to obtain the high-elasticity and high-moisture-permeability TPU film.
Example 4
A high-elasticity and high-moisture-permeability TPU film differing from example 1 only in that the foamed silicone master batch obtained in example 1 was replaced with the foamed silicone master batch obtained in preparation example 4, and the other components, amounts and preparation methods were the same as those of example 1.
Example 5
A high-elasticity and high-moisture-permeability TPU film differing from example 1 only in that the foamed silicone master batch obtained in example 1 was replaced with the foamed silicone master batch obtained in preparation example 5, and the other components, amounts and preparation methods were the same as those of example 1.
Example 6
A high elastic, high moisture permeable TPU film differing from example 1 only in that 100 mesh polystyrene was used instead of 200 mesh polystyrene in example 1, and the other components, amounts and preparation methods were the same as in example 1.
Example 7
A high elastic, high moisture permeable TPU film differing from example 1 only in that polystyrene of 400 mesh was used instead of polystyrene of 200 mesh in example 1, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 1
A TPU film differs from example 1 only in that the silicone master batch obtained in comparative preparation example 1 is used instead of the foamed silicone master batch obtained in example 1, and the other components, amounts and preparation methods are the same as in example 1.
Comparative example 2
A TPU film differs from example 1 only in that a polyether polyol (GE210) is used in place of the perfluoropolyether diol of example 1, and the other components, amounts, and preparation are the same as in example 1.
Comparative example 3
A TPU film was different from example 1 only in that polystyrene was added in an amount of 10 parts by weight, and TPU particles (S90A) were additionally added in an amount of 15 parts by weight, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 4
A TPU film was different from example 1 only in that 2 parts by weight of TPU particles (S90A) were additionally added without adding the foaming silicone master batch, and other components, amounts and preparation methods were the same as example 1.
And (3) performance testing:
(1) moisture permeability: testing according to the test method specified in GB/T2679.2-2015;
(2) elongation at break and 100% recovery from set elongation: the test was carried out according to the test method specified in GB/T528-2009.
The TPU films provided in examples 1-7 and comparative examples 1-4 were tested according to the test methods described above, and the test results are shown in Table 1:
TABLE 1
| Moisture permeability (g/m)2·24h) | 100% elongation at rest (%) | Elongation at Break (%) | |
| Example 1 | 10500 | 98 | 490 |
| Example 2 | 10460 | 98 | 485 |
| Example 3 | 10360 | 96 | 481 |
| Example 4 | 9400 | 93 | 470 |
| Example 5 | 9380 | 90 | 471 |
| Example 6 | 9800 | 92 | 472 |
| Example 7 | 9050 | 90 | 468 |
| Comparative example 1 | 9800 | 80 | 435 |
| Comparative example 2 | 2800 | 90 | 468 |
| Comparative example 3 | 5840 | 92 | 470 |
| Comparative example 4 | 7680 | 87 | 468 |
As can be seen from the data in Table 1, the TPU film provided by the invention has excellent elasticity and moisture permeability.
Specifically, the TPU films provided in examples 1 to 7 have a moisture permeability of 9050 to 10500g/m224 h; the 100% definite elongation recovery rate is 90-98%; the elongation at break is 468-490%.
Comparing example 1, comparative example 1 and comparative example 4, it can be seen that the 100% elongation recovery and elongation at break of the TPU film obtained by replacing the foamed silicone base particle with the silicone base particle (comparative example 1) or directly without adding the foamed silicone base particle (comparative example 4) are both greatly reduced.
Comparing example 1 with comparative example 2, it can be seen that the moisture permeability of the resulting TPU film is greatly reduced by replacing perfluoropolyether diol with a conventional polyether polyol for the preparation of TPU materials.
Comparing example 1 with comparative example 3, it can be seen that the moisture permeability of the TPU film obtained by excessively lowering the amount of polystyrene added in the raw materials for preparation is greatly lowered.
Further comparing example 1 with examples 4 to 5, it can be found that when the silicone powder and the TPU particles in the raw materials for preparing the foamed silicone masterbatch are out of or below the specific range set by the present invention, the moisture permeability, the elongation at break and the 100% elongation at break of the obtained TPU film are all reduced.
Further comparing example 1 with examples 6 to 7, it can be seen that when the particle size of the polystyrene added to the raw materials for preparation is not within the set range, the moisture permeability, elongation at break and 100% proof elongation of the finally obtained TPU film are all reduced.
The applicant states that the present invention is illustrated by the above examples to a highly elastic, highly moisture permeable TPU film and process for making the same, but the present invention is not limited to the above process steps, i.e., it is not meant that the present invention must rely on the above process steps to be practiced. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The high-elasticity and high-moisture-permeability TPU film is characterized in that the preparation raw materials of the high-elasticity and high-moisture-permeability TPU film comprise the following components in parts by weight:
2. the highly elastic and highly moisture permeable TPU film of claim 1 wherein the aliphatic diisocyanate comprises any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, or methylcyclohexane diisocyanate;
preferably, the chain extender comprises 1,4 butanediol;
preferably, the catalyst comprises an organotin catalyst;
preferably, the particle size of the polystyrene is 200-300 meshes.
3. The high-elasticity high-moisture-permeability TPU film as claimed in claim 1 or 2, wherein the raw materials for preparing the foaming silicone master batch comprise the following components in parts by weight:
90-100 parts by weight of TPU particles;
2-10 parts by weight of a foaming agent;
80-90 parts by weight of silicone powder;
preferably, the mass ratio of the TPU particles to the silicone powder is 1 (0.8-1.2);
preferably, the blowing agent comprises any one or a combination of at least two of carbon dioxide, nitrogen, propane, n-butane, isobutane, n-pentane or isopentane;
preferably, the foaming silicone master batch is prepared by the following method, and the method comprises the following steps: and mixing the TPU particles, the foaming agent and the silicone powder, and extruding to obtain the foaming silicone master batch.
4. The highly elastic and highly moisture permeable TPU film of any one of claims 1 to 3, wherein the abrasion resistant additive comprises one or a combination of at least two of polytetrafluoroethylene fibers, molybdenum disulfide, graphite or polyimide fibers, preferably polytetrafluoroethylene fibers and/or polyimide fibers.
5. The highly elastic and highly moisture permeable TPU film as claimed in any one of claims 1 to 4, wherein the UV resistant agent comprises any one or a combination of at least two of salicylate UV resistant agent, benzophenone UV resistant agent, benzotriazole UV resistant agent, substituted acrylonitrile UV resistant agent, triazine UV resistant agent or hindered amine UV resistant agent.
6. The high-elasticity high-moisture-permeability TPU film as claimed in any one of claims 1 to 5, wherein the raw material for preparing the high-elasticity high-moisture-permeability TPU film further comprises any one or a combination of at least two of an antioxidant, a lubricant or a pigment;
preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
preferably, the content of the antioxidant in the raw materials for preparing the high-elasticity and high-moisture-permeability TPU film is 1-5 parts by weight;
preferably, the content of the lubricant in the raw materials for preparing the high-elasticity and high-moisture-permeability TPU 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 raw materials for preparing the high-elasticity and high-moisture-permeability TPU 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.
7. A method for preparing the high-elasticity high-moisture-permeability TPU film as claimed in any one of claims 1 to 6, which comprises the following steps:
(1) reacting perfluoropolyether diol, aliphatic diisocyanate and a catalyst to obtain a prepolymer;
(2) reacting the prepolymer obtained in the step (1) with a chain extender, and extruding to obtain TPU resin;
(3) and (3) melting, extruding, cooling and stretching the TPU resin obtained in the step (2), polystyrene, foaming silicone master batch, an abrasion-resistant additive, an anti-UV agent, an optional antioxidant, an optional lubricant and an optional pigment to obtain the high-elasticity and high-moisture-permeability TPU film.
8. The preparation method according to claim 7, wherein the temperature of the reaction in the step (1) is 70-80 ℃;
preferably, the reaction time in the step (1) is 2-3 h;
preferably, the temperature of the reaction in the step (2) is 40-60 ℃;
preferably, the reaction time in the step (2) is 6-12 h.
9. The method according to claim 7 or 8, wherein the melt extrusion temperature in the step (3) is 170 to 200 ℃;
preferably, the pressure of the melt extrusion in the step (3) is 10-20 MPa;
preferably, the melt extrusion of step (3) is performed by a single screw extruder;
preferably, the rotating speed of the single-screw extruder is 20-100 rpm.
10. The method according to any one of claims 7 to 9, characterized by comprising the steps of:
(1) reacting perfluoropolyether diol, aliphatic diisocyanate and a catalyst at 70-80 ℃ for 2-3 hours to obtain a prepolymer;
(2) reacting the prepolymer obtained in the step (1) with a chain extender at the temperature of 40-60 ℃ for 6-12 h, and extruding to obtain TPU resin;
(3) and (3) melting and extruding the TPU resin obtained in the step (2), polystyrene, foaming silicone master batches, an abrasion-resistant additive, an anti-UV agent, 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, cooling and stretching to obtain the high-elasticity and high-TPU moisture-permeable film.
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| CN117866417B (en) * | 2024-01-10 | 2024-06-07 | 广东中鼎科技发展有限公司 | Waterproof breathable antibacterial high-elastic TPU film for wound care and preparation method thereof |
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| CN107043531A (en) * | 2017-03-14 | 2017-08-15 | 浙江环龙新材料科技有限公司 | A kind of TPU film and its manufacture method and purposes with good rate of perviousness |
| CN109401281A (en) * | 2018-09-11 | 2019-03-01 | 苏州市雄林新材料科技有限公司 | A kind of high-elastic TPU film and preparation method thereof |
| CN112497877A (en) * | 2020-11-27 | 2021-03-16 | 浙江长鸿纺织科技有限公司 | Waterproof moisture-permeable composite TPU film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107043531A (en) * | 2017-03-14 | 2017-08-15 | 浙江环龙新材料科技有限公司 | A kind of TPU film and its manufacture method and purposes with good rate of perviousness |
| CN109401281A (en) * | 2018-09-11 | 2019-03-01 | 苏州市雄林新材料科技有限公司 | A kind of high-elastic TPU film and preparation method thereof |
| CN112497877A (en) * | 2020-11-27 | 2021-03-16 | 浙江长鸿纺织科技有限公司 | Waterproof moisture-permeable composite TPU film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117866417B (en) * | 2024-01-10 | 2024-06-07 | 广东中鼎科技发展有限公司 | Waterproof breathable antibacterial high-elastic TPU film for wound care and preparation method thereof |
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